PHYSICO-CHEMICAL STUDIES ON HEAVY METALS IN INDUSTRIAL WASTES AND RIVER WATER
DISSERTATION FOR M^ittt of $I)tlos!opfip IN CHEMISTRY
BY RUBINA CHAUDHARY
DEPARTMENT OF CHEMISTRY ALIGARH MUSLIM UNIVERSITY ALIGARH (INDIA) 1989 DS1531
/^: F-HJ-VES I CO'—CHEIM I C(=%L- OT'LJFJ T. ESS ON
HEZi^SW METi^^LS I hJ I hJDLJSTR:: I s^^il
W#=IISTIE:S (=mMO RIVER: WftTEFi
A DISSERTATION SUBMITTED IN PARTIAL FULFILMENT OF
THE REQUIREMINTS FOR THE DEGREE OF MASTER OF PHILOSOPHY IN CHEMISTRY
RUBINA CHAUDHARY
Department of Chemistry Aligarh Muslim University
ALIGARH 1989 rnone : unice : t)U4Z
Z. H. College of Engineering & Technology DEPARTMENT OF APPLIED CHEMISTRY Aligarh Muslim University ALIGARH—202002 (INDIA)
Ref. No. Dated
CERTIFICATE
This is to certify that the work des cribed in this dissertation is the original work of Miss Rubina Chaudhary, carried out under my supervision and guidance. She has fulfilled all the requirements for the award of M.Phil, degree under the Academic Ordinaces of the Aligarh Muslim University, Aligerh. The work included in this disser tation has not been submitted elsewhere.
6.11.1989 PROF. MOHAMI^AD AsJl-'-y' ^ Supervisor ACKNOWLEDGEME Hr
I am extremely grateful to my Supervisor Professor Mohansnad Ajmal for his guidance/ advice and personal interest during the course of this work, without whose sympathetic and inspiring attitude, timely assistance and affectionate encouragement this work would not have emerged in its present form. My thanks are also due to Prof. K.T.Nasim, Chairman, Department of Applied Chemistry, Z.H. College of Engineering & Technology, Allgarh Muslim university, Aligarh, for providing necessary facilities. I am grateful to Professor R.H.Siddiqui, Department of Civil Engineering, AMU, Aligarh, who provided instrumentation facilities in his Department. Special thanks are due to Mr. Adil H.Jafri, Deputy Manager, National Newsprint, Pulp and Paper Mills, Nepanagar (M.P.), for providing material and morale for this study. I am also thankful to my senior collea gues, lab. colleagues and friends for their help, discussion and encouragement, I am grateful to Mr. Mashhood Alam Raz who typed the manuscript, and my parents and brothers for their moral support. The financial assistance provided by the Department of Environment, New Delhi, is grate fully acknowledged.
RUBINA CHAUDHARY ii
CONTENTS
List of Tables
GENERAL INTRODUCTION 1 Man and Environment 1 Water Pollution 1. Heavy Metals and Their Health Hazards 11 1.1 Arsenic 12 1.2 Cadmium 13 1.3 Chromium 14 1.4 Zinc 14 1.5 Manganese 15 1.6 Mercury 15 1.7 Iron 16 1.8 Copper 16 1.9 Lead 17 1.10 Nickel 18 2. The Sources of Metal Pollution 18 2.1 Geological Weathering 18 2.2 Mining Effluents ... 19 20 2.3 Industrial Effluents 23 2.4 Domestic Effluents 23 2.5 Urban Storm Water Runoff 24 2.6 Atmospheric Sources
Chapter I SURVEY OF LITERATURE 25 1. Industrial Waste 25 2. Heavy Metal Pollution in Rivers 31
Chapter II MATERIALS AND METHODS 41 1. Collection of Waste Samples ... 41 2. Collection of River water 41 ill
3, Preservation of samples 41 Physico-chemical Analysis 42 Analysis of Heavy Metals 42
Chapter III PHYSICO-CHEMICAL STUDIES ON THE PULP-PAPER MILL WASTE AND EFFLUENT AFTER TREATMENT ... 44
The Factory ... 46 1. Bamboo Sulphate/Kraft Mills ... 47 2. Ground wood process 48 3. Cold Soda Chemi-Mecha- nical Process 48 4. Caustic Chlorine Plant 49 5. Effluent Treatment Plant 50 Results and Discussion 50
Chapter IV PHYSICO-CHEMICAL STUDIES ON GANG A WATER (INDIA) 59
Introduction 59 Results and Discussion 61
REFERENCES 77 iv
LIST OF TABLES
Table 1 Toxic Chemicals in Effluents from Selected Industries 5 2 Characteristics of Industrial Effluents 6 3 Estimated Industrial Water Use 9 4 Metals in Industrial Waste Water 21 5 Physico-chemical Characteristics of Pulp-Paper Mill Waste and Effluent After Treatment 56 6 Concentration of Heavy Metal in the Pulp-Paper Mill Waste and , Effluent After Treatment (rogl~ ) 58 7 Location of Basic Stations 70 8 Physico-chemical Characteristics of Ganges River Water at Various Stations (1987-1988), 71 9 Concentration of Heavy Metals in the Water of Ganga river (Aigl-^) (1987-1988). 75 GENERAL INTRODUCTION
In nearly every corner of the globe man is making increasing demands upon his surroundings and thereby altering his own natural environment and that of the other organisms living with him on the earth. So it is difficult to define environmental pollution and its definition may change not only from country to country but also from area to area within the same country.
MAN AND ENVIRONMENT
The relationship of man with the environment is necessarily symbiotic; the equilibrium between the two must be maintained at all costs. The demands are increasing not only because of the rapid growth of human population but also due to the increase in the standard of living. Acquisition of knowledge about Science and technologies and their application in meeting the ever-increasing needs of man has not left any part of the biosphere untouched, making his own survival precarious. Extensive modifications of the environment have been caused by shifting millions of tonnes of material from one place to another, converting them to less degradable forms or into substances that are positively harmful to living beings. For example hundreds of millions of tonnes of minerals, fuels and other toxic materials are being dug out from the interior of the earth every year and thrown on the earth's surface in one form or the other. Another fact is that this planet has become over-populated. With increasing population, more and more demands are being made on the limited sources of energy and materials. The capacity of the environment to support the increasing demands of man is limited.
The environment performs three basic functions in relation to man. Firstly it provides living space and other amenities that make life qualitatively rich for man. Secondly the environment is a source of agricultural, mineral, water and other resources that are consumed directly or indirectly. Thirdly the environment is a sink where all the waste produced by man is assimilated. It is essential that the capacity of the environment to perform these functions is not impaired^which explains our general concern for it. It is important, therefore, that due to stresses imposed on the environment, the rate of exploitation of resources does not exceed nature's capacity to reproduce them, or that the amount of chemical and industrial effluents do not exceed the assimilative capacity of nature.
Rapid population growth, unplanned towns and random growth of industry are common features of any developing country. Whereas slums, chimneys emitting poisonous gases and deafening noise fall to the lot of city dweller, soil contamination and river and s\ib-soil water pollution due to the use of fertilizers and pesticides are quite common in villages and small towns. Today, fortunately, all sections of society are aware of the problem of environmental pollution.
There is a growing need to tackle the problem through a variety of measures, such as legal, scientific, technical, economic and educational.
The word pollution is derived from the Latin word "pollutus" which means uncleanliness or impurity caused by contamination.
Broadly environmental pollution comprises:
(a) Water pollution (b) Air pollution (c) Land pollution (d) Noise pollution
Water Pollution - Water is one of the most essential constituents of the hxoman environment. Man needs it in the first place for his physiological existence. Just as every other living organism does, and secondly for many other purposes such as industrial water supply, irrigation/ propagation of fish and other aquatic life, generation of power, etc.
Water pollution occurs due to the presence of dissolved inorganic materials, organic materials, such as proteins, fats, carbohydrates and other substances found in domestic and industrial waters, and physical factor such as turbidity, colour, temperature of effluents, associated radio-activity, etc.
Alkalis, acids, inorganic salts and other chemicals formed during processing lead to inorganic pollution. Besides being the cause of corrosion of metals these chemicals are toxic to aquatic life and the organisms responsible for self purification of streams into which the liquid effluents are thrown. Industries like paper and pulp, tanneries, textiles and electroplating are among many others which discharge these chemicals into the watercourses (Tables 1 and 2) . Inorganic chemicals such as free chlorine, ammonia, hydrogen sulphide and other sulphides, salts of metals like Cr, Ni, Zn, Cd, Cu, Ag, etc. are usually found in metal-plating liquid wastes, alkali producing units, polyvinyl chloride, coke-oven and fertilizer industries. Pharmaceutical industries also produce large quantities Table 1
Toxic Chemicals in Effluents from Selected Industries
Industry Toxic Pollutants
1. Electroplating Cyanide and heavy metals like Cr(VI), Zn, Cd, Cu, Ni, etc. 2. Metallurgical Heavy metals like Cu, Cd, Zn 3. Caustic chlorine Mercury 4. Fertilizer Ammonia^ arsenic, chromium 5. Metallurgical coke Phenols, cyanide, thiocyanide and ammonia. 6. Resin Phenol formaldehyde Cyanide, acrylo- and aceto- 7. Synthetic wool nltrite. BHC, DDT, 2,4-D Malathion, 8. pesticides Palathion, etc. Coloured bodies, oxalic acid, 9. Dyes and Pigments heavy metals like Pb, Zn, Cu Phenols, specific toxic 10. Petro-chemicals chemicals not recovered during processing. Table 2
Characteristics of Industrial Effluents
Nature of Pollutants Type of Industry in Raw waste
1. Distilleries Low pH, high orgai^ic contents i.e., BOD, colour and disso lved solids.
2. Tanneries High organic content (BOD), high salt content, deep colour, high concentration of precipitable calcium content.
3. Textiles a) Cotton High pH, sodium content, organic matter and colour. b) Synthetic Low pH, high dissolved solids content and toxic organics.
4. Pulp and Paper Mills a) Pulp mills High pH, deep colour, some dissolved and suspended organics, high suspended inorganics, and large volume of waste. b) Paper Mills High suspended solids (mostly fibre) medium BOD and colour.
5. Dairies High BOD, high colloidal solids, high rate of bio- degradation, grease, acids or alkalies, odour on stagnation.
(Contd.) 6. Slaughter High BOD, colour, offensive Houses odours on stagnation, iron. 7. Antibiotics High acidity or alkalinity and toxic organics.
8, Synthetic drugs High acidity or alkalinity and toxic organics.
9, Organic chemicals High acidity or occasionally high alkalinity, toxic orga nics, toxic metals and salts.
10. Oil refineries petroleum oils in free emul sion or soluble form, acids, alkalies, salts, phenols, soaps and resinous or tarry materials.
11, petrochemicals Mineral oils in various forms, toxic and non-toxic organic acids and alkalies.
12. Fertilizers a) Nitrogenous High pH and ammonia, result ing in toxicity to fish and scorching of plant roots when used for irrigation. b) Phosphatic High fluoride content.
13. Plating shops High acidity and toxic metal or high alkalinity and cyanides.
14. Steel mills a) Coal washeries High suspended solids — mostly coal and ash. b) Coke ovens High pH and ammonia, high monohydric phenol and its derivatives and some cyanides and cyanates. c) Blast High suspended solids — mostly furnaces mineral oxides. d) Pickling Shop High acidity and iron salts. 8
of free acids and neutralized chemicals during different unit processes, Chromates, phosphates, ammonia and urea are typical chemicals found in effluents from fertilizer industries. Pollution due to mercury in chlor-alkali industries has forced the latter to switch from mercury to diaphragm cells in spite of the many operating difficulties of the latter (Table 3),
Organic pollution is due to the presence of high molecular weight compounds such as sugars, oils and fats and proteins obtained from distillery, canning/ sugar and other food-processing industries. They impart a high BOD load to the liquid waste. These organic compounds are readily degraded in aqueous medium by soil and micro-organisms present in the sewage. During this process, dissolved oxygen in the stream is used up. When the dissolved oxygen is reduced below a certain limit, aquatic life is affected adversely. Oil spillage from tankers and ships leads to the pollution of beaches. Some wastes from pharmaceutical and petro-chemical industries, and coke-ovens contain phenols which are toxic to fish.
Turbidity of waste water is caused by the presence of colloidal matter which does not settle readily. This consists of fine clay particles, milk wastes, sewage, free peroxides formed from iron and other Table 3
Estimated Industrial Water Use
Volume of Water Industry used
Dairy 6-10 1/L of milk Sugar 1.5-4.0 1/kg cane crushed OR 15-40 lAg sugar
Distillery 20 1/L alcohol Cotton Textile 1/metre cloth Viscose Rayon 1,600 /lAg fibre Pulp and paper 270-450 l/kg paper OR 270 - 45 m^/ton
Tannery 40-45 1/kg hide processed Integrated steel 20-50 lAg steel Urea 6-8 1/kg urea 10
metal salts, ceramic industries or paper and pulp industries. Turbidity can inhibit the penetration of light, limiting photosynthesis by micro-organisms and thereby adversely affecting oxygenation of the water. Colour pollution is caused by liquid effluents from pickling, paper and pulp, dyd-stuff, tanning and textile industries. Colour in the liquid effluent also cuts off the sunlight required for photosynthesis, use of synthetic detergents and effluents from indus tries such as paper and pulp (containing lignin and lignosulphonates) gives rise to foams that are quite stable due to the presence of surfactants. These foams have the capacity to carry suspended solids as well as pathogenic bacteria. Besides, stable foams make the treatment of liquid wastes highly ineffective. Another form of physical pollution is thermal pollution. This is due to the high tempera tures of liquid wastes from applications such as power stations. When the hot liquid is discharged into a river the temperature of the water increases, thereby decreasing the equilibritun content of dissolved oxygen. Even normally the temperature of water bodies in India is fairly high.
Any additional rise in temperature of the water reduces its oxygen content further. With the organic 11
load from industrial and sewage discharges and the increased biological activity due to high temperatures, oxygen content is likely to get reduced below the critical level. It is most desirable that industrial liquid effluents are pretreated or rid of undesirable chemicals before being thrown on the land and in rivers, seas or public sewers. If discharged into public sewers they can corrode the lives and treat ment equipments as well as reduce biological activity due to the presence of toxic materials.
L Heavy Metals and Their Health Hazards
The heavy metals are probably the most harmful and insidious pollutants because of their non biodegradable nature as well as their capacity of bio-accximulation in the tissue systems. They are potent to cause adverse effect by impairing the metabolic fxinction of the body at a certain level of exposure and absorption.
Zamansky (1974) has classified heavy metals as those metals whose atomic number exceeds 23. Formerly heavy metals were defined on the basis of specific gravity is more than five were considered to be heavy Rietals. The wide differences in the physico-chemical features and toxicological actions of these heavy 12
metals demand a better classification. Many of these elements are essential ingradients of the chemical constituents of the cells and are required to be present in protoplasm in trace amounts. But at high concentrations most of the heavy metals become toxic in action (Luckey et al., 1975). Wood (1974, 1975) with the view point of environmental pollution has classified the heavy metals in three groups:
t> i) Non-critical elements ii) Very toxic and relatively accessible iii) Toxic but very insoluble or rare
The heavy metals, which are of prime concern to environ mentalists and physicians, like mercury, lead, cadmium, copper, are grouped in the second category. Zinc, copper and nickel are reported to have important role in biological system of the body. Copper and zinc play very significant role in metallo-protein synthesis and critical metabolic mechanism. The toxic action of the metal is mainly due to the ionic form of metal present in water (Luoma, 1983). However,the amount of intake of heavy metals in the body depends upon the parameters like pH, temperature, hardness and turbidity etc.(Azeez and Banerjee, 1982).
1.1 Arsenic : Arsenic occurs naturally in all environ mental media and is usually present in the form of compounds with sulfur and with many metals (Cu, Co, 13
Pb, Zn etc.) the levels of environmental arsenic are normally reported in terms of total arsenic (EPA, 1976). Based on human health data« a concentration of 50 jag of arsenic per litre is not associated with any adverse health effects. Estimates have been made of the risk of cancer from low intakes of arsenic, but these are very uncertain. At an arsenic concentration of 50 ;ug/litre, the contribution made by water to the total intake will normally be about one half to two- thirdsy for very low dietary intakes of arsenic, the proportion provided by water may be somewhat higher. Arsenic in drinking water will normally be the main source of inorganic arsenic.
Chronic poisoning of arsenic causes general mus cular weakness, loss of appetite and nausea, leading to inflammation of the mucous membranes in the eye, nose and larynx. An arsenic concentration of 0.05 mg/litre is recommended as a guideline value (WHO, 1984).
1.2 Cadmium : The solubility of cadmium is influenced by the nature of the source of the cadmium and the acidity of the water. It is reported to be one of the most toxic metal to man and animal. Cadmixim caused itai-itai disease (Shimizu, 1972) as it gets accumula ted mainly in hepatic and renal tissues, which cause 14
pathological changes of the hepatocytes of the liver as well as glomeruli of kidney. A guideline value of 0.005 mg/1 of cadmium is recommended (WHO, 1984).
1.3 Chromixim : Chromium (vi) has been found to be much more toxic than chromium (III) . Drinking water could be the main contributor (40-60 %) to the uptake of chromium (VI). The harmful effects of water borne chromium in man are associated with hexavalent . chromium; trivalent chromium, which is regarded as a form of chromium essential to man, is considered practically non-toxic and no systemic effects appear to have been reported. The people living in areas of the world where atherosclerosis is mild or virtually absent tend to have higher chromium levels in tissues than people from areas where the disease is endemic (Schroeder, 1968) .
Hexavalent chromivim at 10 mg/kg of body weight causes liver necrosis and nephritis in man. The lower doses cause irritation of gastrointestinal mucosa and higher doses cause cancer in man (Kaufman, 1970). A guideline value of 0.05 mg of chromixora per litre is recommended (WHO, 1984).
1.4 Zinc : Zinc is an essential element in human nutrition. The daily requirement is 4-10 mg depending 15
on age and sex. Water containing zinc at concentra tion in excess of 5.0 mg/1 has an undesirably astrin gent taste.
Zinc may be considered non-toxic. The low toxicity of zinc and efficient homoeostatic control mechanisms make chronic zinc toxicity from drinking water and dietary sources. Symptoms of zinc toxicity in hximans include vomiting/ dehydration/ abdominal pain and lack of mxiscular coordination (Prasad, 1976) . The guidline value for zinc in drinking water is 5,0 mg/1 based on taste consideration (WHO, 1984).
1.5 Manganese : Kawanura et al (1941) reported an epedimic of manganese intoxication in Japan resulting from the consumption of contaminated well water. They have reported neurological symptoms and death of two patients whose tissues were found to contain high level of manganese.
At levels exceeding 0.15 mg/litre manganese in water supplies stains plumbing fixtures and laundry. At higher concentrations, it causes an undesirable taste. The guideline value of 0.1 mg/litre is based on its staining properties (WHO, 198^),
1.6 Mercury ; Mercury is a toxic metal and has no beneficial physiological function in man. The 16
presence of mercury in water has become of particular concern since it was found that organic mercury gets accximulated in fish. Elevated mercury levels have been found in fresh water fish taken from areas with suspected mercury contamination and such fish are xinacceptable for hviman consximption. However, mercury in drinking water is predominantly in the inorganic form,which is only poorly absorbed.
According to Krasovsky (1981) mercury causes gonadotoxic and disturbs the metabolism. Women suffer from miniroata disease due to tetragenic effect which were partially present in fetuses. 0.001 mg/L is recommended as the guideline value (WHO, 1984).
1.7 Iron : Iron is an essential element in human nutrition. Hence it is required to be present in body in trace amount. But it becomes highly toxic when ingested in large quantities results in a condition known as haemochromatosis.
The presence of iron in drinking supplies should not be more than 0.3 mg/L because it causes iron stains laundry and plumbing and also undesirable taste in beverages.
1.8 Copper : Copper is an essential element in human metabolism (VWO Technical Report Series, 1973) and is 17
generally considered to be non-toxic for hximan being. Intake of large doses by man lead to severe mucosal irritation.
At levels above 5 mg/l,it also imparts a colour and a undesirable bitter taste to water. Staining of laundry and plumbing fixtures occurs at copper concen trations above 1.0 mg/litre.
The guideline value is 1.0 mg/litre based on its laundry and other staining properties (WHO, 1984).
1.9 Lead : At least two approaches can be combined to form a basis for defining a guideline for the level of lead in drinking-water; one recognizes the contri bution made by drinking water to the level of lead in the blood and the other takes account of the provisional tolerable weekly intake of 3 mg of lead per person established in 1972 by the Joint FAOA«iO Expert Committee on food additives. Lead in high doses causes tiredness, abdominal discomfort, anaemia and in the case of children, behaviour changes have also been observed.
Thus, based on these various considerations and allowing for some margin of safety, a guideline value of lead is 0.05 mg/1 of water is jrecommended (WHO, 1984) . 18
1,10 Nickel : Levels of nickel in drinking water of 5 mg/1 did not produce toxic effects in long term studies in rodents. Nickel compounds can result in allergic effects, primarily in eczematous patients, but such effects are probably more relevant to dermal rather than to oral exposures. The toxicological data available at present indicate that a guideline value for nickel in drinking water is not required.
2 The Sources of Metal Pollution
The problems arising from toxic metal pollution of the environment due to the increasing use of a wide variety of heavy metals in industry and in our daily life, have assximed serious dimensions. In general/ it is possible to distinguish between different sources from which metal pollution of the environment originates, These sources have been described below:
2.1 Geological Weathering i This is the source of baseline or background level. It is to be expected that in areas characterized by metal-bearing forma tions, these metals will also occur in elevated levels in the water and sediments of the particular area. Obviously mineralized zones, when economically viable, are exploited retrieve and process the ore. This in 19
turn leads to disposal of tailings, discharge of effluents and possibly smelting operations which result in atmos pheric pollution.
Arsenic hot springs arising from geothermal activity feed the Waikato River of North Island, New Zealand, Submerged aqxiatic plants from this river were found to contain a maximum of 650 mg kg~ of dry mass as compared to arsenic levels below 12 mg kg" in plants, growing in natural soils (Reay# 1972).
2.2 Mining Effluents
The serious effects of mine effluents on the ft water quality in rivers and lakes, as well as on the biotopes, particularly on the fish population, have been known for many years. One of the very first descriptions of this problem is the fifth report of the 1868 River Pollution Commission (Anon, 1874) in Britain, where especially grave damage was caused by the dispersal of toxic metals from lead, zinc, and arsenic mines in Mild-Wales (Lewin et al., 1977). Mine drainage does not occur only from the mine itself but also from waste rock dumps and tailings areas. The latter two sources often contain a high concentration of sulfides and/or sulfo salts which are associated with most of the ores and coal bodies. 20
2.3 Industrial Effluents
There are nximerous of Industrial effluents lead ing to heavy metal enrichment of the aquatic environ ment. The classic example is the discharge of the catalyst methylated mercury chloride into Minamata Bay from a factory manufacturing plastics.
Chemicals and electrochemical methods are employed in the metal finishing and allied industries for the purpose of protection and/or the decoration of a variety of metal surfaces (e.g., Lowe, 1970). Most of the processes are followed by rinsing operations to remove the excess chemicals and other waste materials from the treated surface, thus giving rise to effluents. Notably, pickling and electroplating give rise to high waste metal concentrations. Obviously, most effluents from pickling and dipping operations are strongly acidic and contain an appreciable amount of dissolved metals. It has been estimated that the Dow Chemical chloj>alkali plant at Sarnia has discharged 91,000 kg of mercury compounds into the St.Clair River system from 1949 to 1972 (Wood, 1972).
The principal source of chromium results from the discharges of ind\istries using large amounts of chromate or dichromate as in the textile industry and the leather tanning indxistry. Polish tannery wastes from chrome tanneries have been reported to vary 21
between 9 and 140 rngf (Koziorowski and Kucharski, 1972) .
The environmental pollution from Cd and Zn dis charged from a Braun txibe (used in T.V. sets) factory in Japan was investigated by Asami (1974). The slag at the waste water outlets and settling tank was 4820-5400 and 15,500-3780 ppm respectively.
A typical example of pollution caused by the iron and steel industry is presented by the steel works near the Tees Estuary, Scotland. The so-called elevelent effluent from the Teesside Steel Works (British Steel Corporation)was monitored (Prater, 1975). It was found that iron and manganese had the highest mean concentration. The blast furnaces and the ferroman- ganese plant respectively being the major contributors.
Apart from metal containing discharges by electro- plasters, an inspection of the Table 4 (Klein et al., 1974) reveals that the laxindries as well as ice-cream ^nd soft drink manufacturers also discharge wastes which are rich in copper. The textile dyeing and laundry wastes have high chromium contents. The bakery waste water contains high levels of nickel and the fur dressers and dyers discharge exceptionally high concentrations of Cu, Cr, Ni, Zn and cd (Table 4) (Klein et al., 1974). 22
Table 4
Metals In Industrial Waste Water (Klein et al., 1974)
Average Concentration in AIQT Industry Cu Cr Ni Zn Cd Meat processing 150 150 70 460 11 Fat rendering 220 210 280 3,890 6 Pish processing 240 230 140 1,590 14 Batery 150 330 430 280 2 Miscellaneous food 350 150 110 1,100 6 Brewery 410 60 40 470 5
Soft drinks and 2,990 3 flavorings 2,040 180 220 Ice cream 2,700 50 110 780 31 Textile dyeing 37 820 250 500 30
Fur dressing and 7,040 20,140 740 1,730 115 dyeing
Miscellaneous 800 27 chemicals 160 280 100
Laxindry 1,700 1,220 100 1,750 134 Car wash 180 140 190 920 18 23
2.4 Doroestlc Effluents
The domestic waste water constitute the largest single source of elevated metal values in rivers and lakes. Solid waste water particles may cause metal enrichment of the suspended load in the waters. The concentrations of copper, lead, zinc, cadmium and silver reveal a marked influence of domestic effluents in the receiving waters (Prexiss and Kollmann, 1974),
The use of detergents also creates a possible "pollution hazards, since common house-hold detergent products can affect the water quality. Angino et al. (1970) found that most enzyme detergents contain trace amounts of the elements Fe, Mn, Cr, Ni, Co, Zn, Sr and B,
2.5 Urban Storm Water Runoff
With regard to pollution resulting from the urbanised areas, there is increasing awareness that
urban xninoff presents a serious problem of heavy metal contamination. Heavy rainfall in urban areas is no longer regarded as only a downpour of "rain water* (Sartor et al., 1974) since they often contain shock loads of contaminants. A statistical sxammary (Bradford, 1977) revealed that urban stormwater runoff has long been recognised as a major source of pollutants to 24
surface waters.
The potential contamination may occur during periods of storm runoff whereby trace elements result ing from atmospheric emissions and subsequently depo sited on various surface material to the nearby drainage system. After monitoring heavy metals from two heavily urbanized watershed at Lodi, New jersey, Whipple and Hunter (1977) established high concentrations of lead, zinc and copper after storm event.
Atmospheric Sources
Natural and man made processes have been shown to result in metal containing air-borne particulates. Depending on prevailing climatic conditions, these particulates may become wind-blown over a great distance,nonetheless they are sxibjected to the fate that they are ultimately returned to the lithosphere through rain or snowfall.
A recent study has revealed that 15-36 % of the Pb entering Lake Ontario from the Niagara River was attributable to atmospheric precipitations (Shiomi, 1973). Chapter I
SURVEY OF LITERATURE
1, Industrial Waste
Cullen et al. (1982) have removed heavy metals from the metallurgical processing and electroplating wastes, by contact with ion exchange media produced by treating brown coal, peat or saw dust with aqueous lime slurry. They obtained the following metal concen trations Hg 0.0005; Cu 0.02, Zn 0.02, Cd/L0.05, Pb 0.1 and Mn 0.2 mg/L by using calcium loaded brown coal as the extracting medium.
Angelova et al. (1980) have studied the removal of heavy non-ferrous metals from lead - zinc plant waste water by extraction. The higher fatty acids C -C ) were used for these extractions.
A waste water containing Hg was treated with copper salt and iron powder in acidic medium, Hyogo prefecture (1982). The solids are then separated by filtration and the supernatant liquid was adjusted to pH 10-11 for further filtration and neutralization for Hg removal. They observed in this treatment process that a waste Water containing 520.0 mg Hg/L was mixed with a
25 26
copper salt, adjusted to pH 2 and mixed with iron powder, found to contain Budilovskii et al. (1983) suggested that metals get precipitated from waste water as hydroxides at pH 8.75-9.25 with subsequent separation of the precipi tation and neutralization of the effluents to pH 8.5. They also found that the residual concentration of metal get further reduced by treating the waste water with iron hydroxide (50-250 mg/L). Teshchina et al. (1982) get success in removing small concentrations of Sb(III) from waste water by adsorption on hydroxide apatite precipitates in presence of calcium and phosphate with /»^ 100 % preci pitation at pH /N^12.0. They also found that the presence of chloride or nitrates at 15-20 mg/L does Rot interfere, whereas fluoride and sulphate decreased the adsorption of Sb(III). Sloan et al. (1984) studied the removal of metal ions from wastewater by the help of 3 algal species with a concentration factor. Su and Lou (1983) have suggested the method of treatment of zinc-containing waste water with neutra lization-coagulation and precipitation. Zinc was treated with NaOH to adjust pH values to 8 + 0.5 for coagulation- precipitation. 27 Chrome-plating waste was treated with lignite and the concentration of Cr(VI) was found to decrease rapidly at low pH and at high temperature. The Cr(VI) ion adsorption on lignite was found to be greater than Cr(III) ions (Nishimura, 1984). Tan et al. (1985) have studied the uptake of metal ions by chemically treated human hair. They found the uptake capacity as Hg (Hg ) ^ Ag > Pb \ Cd > cu (Cu ) > Cr ^ Ni . The presence of other metal ions have been found to greatly affect the capacity. The adsorption of a single metal ion was affected very little by the type of anion associated with it, but has been found to be more pronounced for mixed metal ions. Loizidou et al. (1985) have studied the removal of heavy metals by natural zeolites. Clinoptilolite and mordenite have similar exchange capacities (2,19 and 2,11 mequiv/gm respectively). They observed that clinoptilolite has higher exchange capacity than mordenite in the removal of Cd and Pb from waste water. The maximum exchanged capacity of clinoptilolite and mordenite for Cd was 0.66 and 0.33 respectively, and 0.8 and 0,33 for Pb respectively. Trivedi and Khomane (1985) have studied the removal of nutrients from distillery, cotton textile 28 and metal working waste water by water hyacinth. Odozi et al. (1985) carried out the sorption of heavy metals with corncobhydroxylate red onion skin 2+ 2+ 2+ 2+ resins. The removal for Pb , cd ^ Zn , Cu 2+ and Hg have been found to the extent of 94.6, 91.4, 90.6, 86.4 and 82.8 % respectively. The maxiraxun capacities per gram of the substrate were 1.09, 1.41, 1.39 and 1.21 mequiv, for Zn^"*", Cu^"*", Ca^"*" and Pb^"*" respectively. Kato et al. (1986) studied the removal of heavy metals by adsorption from the waste waters. Two litres of waste water containing —50 ppm each of 2+ 2+ 2+ Cu , Zn and Pb were mixed with 0.2 mol FeSO, and pH of the mixture was adjusted to 10 and stirred for 4 hours. Barium ferrite was added to the resulting solution to precipitate heavy metals. The super natant liquid was found to contain Cu 0.05, Zn 0.03, Pb 0.1 and Pe 0,07 ppm. Suemitsu et al. (1986) suggested sawdust coated with reactive dye, procion-red or procion-yellow for removal of many metal ions from aqueous solution. They found that the solutions containing -^100 ppm of metal ions were used in batch andcolumn experiments. The adsorption was found to be pH dependent and indepen dent of temperature. 29 Bower et al. (1986) reported that when waste water containing cr(yi) were treated by reduction with Iron filings at a pH of 5,5-10.5 resulted In an effluent with Cr(OH)_ concentration exceeding the theoretical solution of Cr(OH)-at a j>H of < 5,5. This shows that Iron hydroxide precipitated during the process, improved the coagulation and settling of the Cr(OH)- and decreased Cr(III) ions, A comparison of data from coagulation and settling of the Cr(III) already In waste water by NaOH and Ca{OH)- with the data on the removal of Cr(III) formed by the reduction of Cr Chalakhappllly et al. (1987) have studied the ranoval of mercury from Industrial wastes by adjusting pH. The residual Hg was found to be ;< 0,01 mg Hg/L. Bhargawa et al. (1987) reported the removal of heavy metals, e.g., Cr, Pb and Cd, from synthetic waste 'water by adsorption. They used sawdust to removed low concentrations (1-5 mg/L) of heavy metals (Cr, Pb and Cd). The efficiency of removal was determined by the metal concentrations, the amount of saw dust and the contact time. They found that at higher the metal concentrations (>10 mg/L) lower was the efficiency of removal. They found that Cr was more efficiently 30 adsorbed than Pb and cd. Acidic waste waters (pH 2.2) from petroleum refining catalyst manufacture containing Fe 36, Cu 41, Mo 29, and Zn 22 mg/L were treated with milk of lime to adjust pH 5.5-6,5. The precipitate was separated by settling and the effluent was neutralized to pH 8.0-8.5. The metal removal > 95 % was obtained (Abdrakhimov, 1988). Tee et al. (1988) have reported that waste tea- leaves were good sorbent for Pb, Cd and 2n ions. The extent of adsorption depends on pH, ionic strength, metal concentration, stibstrate concentration and the presence of interfering ions and surfactants. They observed that the adsorption capacities of tea leaves were 0.381, 0.28 and 0.18 romol/gm for Pb, Cd and Zn respectively. The relative affinities of metal ions towards waste tea leaves was in the order of Pb> Cd> Zn. Waste Water from cadmium sponge manufacturing factory was treated with sodium sulphide to remove Mg, Al and Cd. The treated waste water was deionized and recycled to the plant. The treatment of waste waters from the regeneration of ion exchanger columns was also described (Nagy et al., 1988). Mashima et al. (1988) have studied the mercury removal from waste water by activated carbon. The 31 treated HgCl^ soln (1 mg Hg/L) by activated carbon (ccx:onut husk) in the presence of 0.1 % NH OH at pH --'2 for 9 hours. They found that the method was suitable for Hg removal from an acidic waste water containing Na2S0^ KNO^ or sodium tartrate at pH 7.0. The spent carbon was regenerated by elution of Hg with 1 M HNO^ or 5 M ^2^^^' 2. Heavy Metal Pollution in Rivers A class of pollutants requiring particular attention in the aquatic environment is heavy metals. Heavy metals occur naturally in the aquatic environment. In addition* the heavy metals enter the aquatic systems by the direct discharges of industrial and urban effluents, surface runoff and indirectly from aerial fall out. The common feature of the heavy metals is that they are toxic at high concentration but some are highly toxic even at lower concentrations and are readily concentrated by aquatic organisms and plants. The seriousness of heavy metal contamination is further compounded by the fact that they are generally water soluble, non- degradable, vigorous oxidising agents and are strongly bonded to many biochemicals inhibiting their functions. The behaviour of iron, manganese and zinc in a 32 heavily polluted river estuary system was studied by Burell (1979). The preliminary survey was made immediately before the rainy season, when the river flow was minimxiTO. Iron was found in the upstream from the zone of urbanization largely in particulate form. The higher concentrations of Fe, Mn and Zn were found complexed organic form and soluble within the estuarlne mixing zone downstream from Taichung. Metal pollution of Sunter river (Indonesia) Pande and Das (1980) studied the metallic contents in water and sediments of Nalnital lake. The metals Cu, Co, Zn, Pb, Mn, Li, Na, K and Ca were analysed by atomic absorption spectrophotometer in the lake water and sediments at five different sampling stations. The levels of metals in the bottom sediments were found to be much higher than those in the water. The distribution of Pe, Mn, Zn, Cu, Pb and cd among river water, suspended matter and bottom sediments was investigated by Terajima et al. (1980) and they found the physico-chemical states of metals. They 33 ' observed that the metal distribution in the river depends upon the organic substances. Most of the heavy metals dissolved in river water are combined with the soluble organic svibstances. Their physico- chemical state was influenced by the characteristics of the organic substance present. The heavy metal content of waters, and sediments of the Innersts Soese and Sieber rivers, Germany, were given and discussed in relation to waste water dis charge to the rivers (Fytianos, K., 1982). Zhao (1982) compared the heavy metal contents for Pb, Zn, Cu and cd in the Zhujiang river which were 77.39, 43.62, 12.13 and 0.08 AigA respectively. Pb, Cu and Gd in the Xiangjiang river were foxind to be 32, 30.03 and 1.46 Aag/L respectively. The total and the suspended metal contents in the xiangjiang river were well correlated with the correlation coefficients^ viz., 0.98-0.99. The correlation coefficient for Pb was 0.98 and Cd 0.27 in the Zhujiang river. Trace elements concentration in river water of Dagestan and their importance were studied by Getsev et al. (1981) and was edited by Salmanov, A.B. Akad Nauk, U.S.S.R. Dagest Fil Makachkala U.S.S.R. based on chemical compound and mineralization. 34 Paul and Pillai (1983) have studied the distri bution of trace metals in tropical river environment. The fluvial concentrations of trace metals increased in water and decreased in sediments in the Periyar river, Kerala, India, during summer due to soltibili- zation and concentration by evaporation. The levels especially of 2n and Cd increased ten fold both in water and sediments in the industrial zone, Soliobili- zation in the backwater zone under high salinity was one of the major mechanisms of trace metal transport to the marine environment. River meandering was respon sible for large scale deposition of suspended solids in the industrial zone during the monsoon period. Gebhardt et al. (1983) determined pb, Zn, Cd, Co, Cu, Cr, Ni, Pe and wn by atomic absorption spectro scopy in the Water fronts sediments of the lower reaches of Weser river. West Germany. These metals were concentrated in the river water from industrial effluents and emitted before being absorbed by the sediments. Knoeehel et al. (1983) with thirty-three research groups employed seven different methods for heavy metals determination in Elbe river water. The relative standard deviation was found 7-50 % for most of the elements with higher values for Cr and As (130 %) and Pb, Br, Ni, Hg and Cd (60-80 %). 35 The concentration of heavy metals in the waters of Tiber river and in waters of the coastal area surrounding the mouth were determined by Melchiorri et al.(1984) which showed that the river caused sig nificant pollution in the near shore as well as some in the offshore areas. Pappalardo et al. (1983) have studied the concen tration of B, Ba« Ca, Fe, K, Li« Mg, Na» S, Si, and Sr in Alcantara river,Sicily. Several metal or elements increased in concentration as the water moved downstream. These concentrations also increased with time with the highest values generally found in the sanples collected in July 1982. The concentration of Cd, Co, Cr, Cu, Pe, Mn, Ni, Pb and Zn in the water and the sediments of Yamuna river, India, were determined by Ajmal et al. (1985a) . The data showed that there was considerable variation in the concentration of metals from one sampling station to the other which may be due to the variation in the quality of industrial and sewage wastes being added to the river at different sites. The heavy metal contents in acidic rivers in the Nagano prefecture, Japan, were investigated by Katsuno et al. (1984) . The highest concentration was 36 of Fe at 7.9 mg/L (maximtim) , Cd, Pb, Cr(VI) , Cr, As, Hg and Ni were below the water quality standard. As in the sediment was 25 mg/kg (median) and was higher than in other rivers. The total content of Fe, Mn,Co, Ni and Zn in the mixing zone of the Razdalonaya river and Amursky Zaliv, U.S.S.R,, was studied by Filonov (1985). The metal content decreased with increasing water salinity. The dissolved phase of the water was characterized by the redistribution of metal migration forms. For all metals, the fraction of the inorganic form in the estuarine water increased from the river water to sea water, whereas the concentration of metal chelates was found to decrease. Ag, B, Cr, Cu, Fe, Mn, Pb, Ti, V and Zn concentrations of waters and sediments of the Sirava reservoir and the Cirocha and Laborea river, Czecho slovakia, was compared by Pliesovska (1985). The concentration of Fe exceeded the limiting values. The sediments of the reservoir has higher metal concentrations than those of the river, but could still be considered unpolluted. Yoneda et al. (1984) have studied the contribu tion of domestic waste waters to heavy-metal pollution 37 of the river in Nara city, Japan. Sediment samples were collected at polluted points by domestic waste waters and Pollution-Free points and analyzed for heavy metal and total organic carbon. The heavy metal concentration exhibited a log-normal distribution at pollution-free points respectively, Betti et al. (1985) have studied the source of metal (Cu, Pb, Cd, Cr) pollution in Tyrrhenian river and sea water of S. Rossore Park (Pisa). The content of Ph, Cu and Cd was always found higher in the river water than at the reference station. Generally reaching maximum values around the mouths of the rivers Cd concentrations exceeded the minerals risk levels. Chromium concentration was found always below the detection limit. Thxas rivers were found to be the main sources of metal pollution in coastal waters. Liang et al. (1985) determined the concentration of Pb, Hg, Cd, Cr, Cu and Zn in Ta-Chia river water. The samples were analysed by anodic stripping voltammetry, differential pulse polarography and atomic absorption spectroscopy. The samples were taken just above and below the Pu Tzu, Kou water works during the period March to May, 1984. Deheon et ai. (1986) have studied the organic 38 pollutants and heavy metal and compared them In the Mississippi river. The water samples were collected along the entire length of the rivers, and were screened for semi-volatile organic matter by capillary gas-chromatography and for heavy metals by atomic absorption spectrophotometer. Kralik and Sagar (1986) have studied the concen tration of As, Cd, Cr, Cn, Hg, Ni, Pb and Zn in the sediments collected at eight different sampling stations from the Danube river, Austria. The concen- trationsof As, Cd, Cr, Cu, Hg, Ni, Pb and Zn were found to be 10-32, 0,3-3.2, 90-205, 40-135, 0.4-3.3, 42-115, 20-140 and 95-829 ppm respectively. Suzuki et al. (1987) determined the concentration of trace elements (Ca, As, Sb, Sr, Al, Mg, V, Ba, Zn and Rb) in the Tama river, Japan. The concentration of trace metals have been found to be almost the same throughout the entire drainage system, whereas Br, Ni, Mn, Fe, Co, Cl, K and Na concentrations were found to increase from the upper to the lower reaches of the river. The pollution load on the Ganga river was inves tigated by Mathur et al. (1987) at nine different sampling stations in Varanasi region covering a distance of 12 km. The data indicated the presence 39 of the heavy metals such as Cu, Pb, Cd, Cr, Ni, Mn, Zn and Co mainly at the confluence with the sewers. The concentrations of Cd* Pb, Cu and Cr were determined by Gorbi and Campanini (1987) in water and the sediments from Parma river (Italy). Heavy metal concentration in the sediment was found in good agreement with the characteristics of drainage area. Ajmal et al. (1987) have studied the concentration of Cd, Co, Cr, Cu, Pe, Mn, Ni, Pb and Zn in the water and sediments of the Ganges river by atomic absorption spectrophotometry. The ranges of concentrations of Cd, Co, Cr, Cu, Fe, Mn, Ni, Pb and Zn found in the water were ND-0.53, ND-4.89, 3.20-56.6, ND-27.57, 22.0-133.8, 35.0-93.0, ND-2.22, 2.0-5.6 and 7.37- 67.36 Aig/L and in the sediment were ND-3.48, 2.35-14.4, 9.0-83.16, 11.27-95.0, 2168.0-1164.8, 110.5-470.0, 3.45-28.80, 0.55-21.8 and 72.0-418.6 /Ug/g respectively. The distribution pattern of heavy metals was studied by Jo Kota et al. (1988) based on atomic absorption analysis. They collected 172 samples of the bottom surface deposits from the Shinji Lake, Japan, in July through August, 1982. They found the maximum concentrations of Pb 54, Zn 163, Ni 60, Co 20 and Mn 3,5 ppm. The concentrations of the 40 metals except for Mn were found lower near the shore. They suggested the fact that the distribution pattern of heavy metals was related to grain size of the bottom sediment and/or water quality of the inflowing rivers. The Mn concentrations may be affected by dissolved oxygen in the bottom water. Chapter II MATERIALS AND METHODS 1. Collection of Waste Samples Representative grab samples of the individual waste streams were collected at every eight hours for a period 24 hours« and finally made composite sample in proportion to the flow at the time of sample collections. 2. Collection of River Water At each station a composite sample was made by collecting four grab samples at half an hour interval from 30 cm below the water surface in mid-stream, 3. preservation of Samples For physico-chemical analysis sample was freezed while for heavy metal (except mercury) Samples were collected in polyethylene containers and acidified with 6N HNO- so that pH was maintained at about 2.0. Samples for mercury analysis were collected in coming glass bottles (500 ml) and 2.0 ml of 4M HNO. and 5 ml of 2.5 % K2Cr20_ solution prepared in de- ionized water was added as preservative immediately after sample collection. 41 42 Physico-chemical Analysis Physico-chemical parameters were determined according to 'APHA Standard Methods (1985). Dissolved oxygen^ pH, alkalinity, acidity and temperatures were measured on the site by portable kit (Century - CK 704) whereas total solids, sxispended solids, dissolved solids, biochemical oxygen demand, chemical oxygen demand, chloride, sulphate, total phosphorous, total hardness, turbidity, electrical conductivity, ammonia- nitrogen, nitrogen nitrate, nitrogen nitrite were determined in laboratory. Analysis of Heavy Metals For analysis of metals except mercury, nitric acid digestion technique was followed. In this technique, a measured volume of sample (100 ml), nitric acid was added and this solution was brought to slow boiling in order to evaporate to the lowest volume (10-15 ml) possible before precipitation and salting out occurs. An additional amount of nitric acid was added if required and heated gently until the digestion was completed, shown by appearance of clear solution. Now the content and cover should be washed with de- ionized water and filtered through VQiatman filter paper No. 42 to remove silicate and other insolxible material 43 that could clog the atomiser. The filterate should be transferred to volumetric flask with two-three 5.0 ml portions of water. These rinse were also added to volumetric flask which was then cooled and made upto mark. This may be used for analysis by Atomic Absorption Spectrophotometer (Model GBC 902). Mercury analysis was done by using cold vapour Atomic Absox^ption Spectrophotometer (Mercury Analyzer MA-5800D). For processing of samples, 50 ml of sample was treated with 10 ml of HjSO. (1+1), 5 ml nitric acid (cone) and 5 ml KMnO. (5 % W/V) in an Erlenmeyer Reaction flask and kept over night. The excess of KMnO. is reduced by addition of 6 ml of Hydroxylamine Hydrochloride (12 % W/V) is added, shaken vigorously and make upto 100 ml. 1.0 ml of this solution is taken into the reaction vessel of cold vapour AAS to this 2 ml SnClj (20 % W/v in HCl) should be added and stirred for 5 min. When the reaction was completed, the mercury vapours passed to absorption cell and absorbance was recorded. Chapter 111 PHYSICO-CHEMICAL STUDIES ON THE PULP-PAPER MILL WASTE AND EFFLUENT AFTER TREATMENT 1. Introduction The discharge of heavy metals which are non-bio degradable pollutants often contained in the industrial waste water has been the subject of great concern in recent years. The heavy metals cause adverse effects on the living organisms whereas some are lethal even at very low concentration. Therefore, the presence of such substances in water beyond permissible levels is definitely hazardous and render the water unfit for benificial uses. Pulp and paper industry is one of such major industries in India contributing to water pollution. Many varieties of writing, printing, packing and cigazrette paper, straw board and paper board are manu factured in the country. The estimated consumption of water in the pulp and paper mill in India is about 230 3 to 500 M per tonnes of paper produced. Due to its large water requirement, the pulp and paper industry is generally located in the vicinity of a river. The quality of raw water required for the industry is expected to 45 conform to IS-2724. Equally large quantities of waste water are generated in the pulp and paper industry, Daneshwar et al.(1982) studied the Titaghur paper 3 mill in West Bengal, which produces 54,960 M waste water per day. Two main channels located under-ground discharge the plant's waste water into the nearby estuairy. They found the pollution load of the waste water as BOD 136-165, COD 268-480 and suspended solid 494-602 mg/L. The sludge thickening removes the 55 % of the total suspended solids in a detention period of 50 minutes. Balchand and Nambisan (1986) studied physico-chemical p^ameters before and after the commencement of effluent discharge from pulp and paper factory into Muvattupuzha river (India) . Klee (1983) studied the stepwise development of the waste water treatment in a pulp and paper mill over a period of 24 years. Purwati Sri (1985) suggested the utilization of fungi for the decolorization of pulp and paper waste Waters. The result showed that amount of carbon sources added to the sxibstrate and the incubation period had significant effect on the reduction of colour and changes in BOD and COD values. Liu et al,(1988) have 46 found that the aquatic plants including water hya cinth, water peanut, water lily and duckweed are effective for COD removal from pulping waste water in oxidation pond treatment. These plants are especially effective in waste water decolorization. Soetopo (1984) studied the effectiveness of alum and chlorinated copper as coagulants for pulp and paper mill effluent treatment on the laboratory scale. The experiments showed that the dosage applied to the treatment gave significant reduction of physical and chemical pollutant parameters such as sus pended solids, BOD, COD and colour. The Factory The National Newsprint and Paper Mills Ltd. is situated at Nepanagar on the bank of river Tapti about 20 km away from Burhanpur (M.P.) . The effluent is of dark brown colour and also has got high COD, BOD and suspended solids. Pollution from a paper making process originates mostly from the pulping process. The waste water generation depends upon the capacity of the plant and the (juality of paper 47 being produced. The present study of physico-chemical characteristics of effluents of pulp and paper mill at Nepanagar has been under taken in order to assess the performance level of the treatment plant and to find out the water quality of the effluent in view of the specified standairds. Raw Material The raw material generally are the bamboo and salai wood. Apart from the wood, paper cutting/secondary fibres are also used as raw materials for the manufacture of paper. Manufacturing, process Flow diagram of the processes being adapted in thft factory is given in figure 1, and a brief des cription of manufacturing process is given below: 1. Bamboo sulphate/Kraft mills - Bamboo wood is cut into small pieces and washed, screened and digested with sodium hydroxide and sodium sulphate, followed by steaming upto 11 kg/cm at 170°C. The whole cycle is completed in 5-6 hours. The binding material in the wood, lignin and other compounds are dissolved in the cooking liquor. The spent liquor, called black 48 liquor. Is concentrated In evaporators and burnt In a furnace for tlje recovery of chemicals which are reused In the process. The heat generated during combustion Is recovered In the form of steam. The pulp Is recovered from the digester by vacuxim filtration and continuously washed by a spray of water. The wash water always contains the liquor adhering to the cake and contributes to the pollution load. The llcjuld Is called brown stock wash water and Is alkaline In character as It contains part of the original cooking liquid. The molten residue of inorganic chemical is dissolved in water to give green liquor. The green liquor Is treated with lime to convert sodium carbonate to sodium hydro xide. The calcixim carbonate Is calcined In a rotary kiln for reuse. 2. Ground Wood Process - This process consists of debark ing the salai wood and then pulping it by grinding against a rough and abrasive surface, using large quantities of Water. This method makes maximtom utilisation of the wood as dissolution losses are kept low. The pulp produced is mainly used for making newsprint quality paper. 3. Cold Soda Cheml-Mechanical Process - The raw 49 materials (50 % salai wood + 50 % bamboo chips) are digested with NaOH in rotary digesters at a pressure 2 of 11 kg/can maintained with steam. It is a 3-4 hour cycle. The chips are then dunked in live bottom where spent liquor is strained and reused. Chips are refined by two stage refiner and then screened in rotary screen. Finally the stock is cleaned three stage centricleaners and deckered to make 10 % consistency pulp. Pulp is bleached by 8-10 % calcium hypo-chlorite by retaining it for 2 hours in hypo-towers and finally washed and refined by 3 stage refiner. The stock is then ready to be used for paper making. 4*^. Caustic Chlorine Plant - Raw salt is fed into open brine saturators. The brine solution is pumped to classifiers where flocculation agents are added. The brine solution is adjusted to 4-5 pH and fed to the Krab cells. Electrolysis takes place in primary cells and sodium amalgam is formed and sent to secondary cell where chlorine is evolved and sent to dichloricators and brine saturators. The amalgam in secondary cell is treated with soft water whereby NaOH is formed and collected and stored. Hydrogen evolved is partially used for HCl preparation and rest vented to atmosphere. 50 3 5. Effluent Treatnvent Plant (capacity 330 M /hr) Effluent treatment plant consists of clarifiers, 3 an aerobic lagoon of 1,40,000 M and aerobic lagoon of 3 9,600 M with aerators, sludge handling system and dry ing beds. The treated water is released in Tapti river. The samples from the complex were collected at three stations, viz.. A, B and C. Description of each sampling station is given belowt 1 A Chemical pulp mill 2 B 1. Mechanical pulp plant 2. Cold caustic soda pulp plant 3 C Effluent after final treatment. Results and Discussion The physico-chemical properties of the effluents of the National Newsprint and Paper Mills Ltd., Nepa- nagar (M.P.), are given in table 5. The effluent satisfies the limits in relation to parameters such as alkalinity, ammonia-nitrogen, nitrate- nitrogen, nitrite-nitrogen, phosphate, sulphate, total hardness, calcium-hardness, electrical conductivity, and dissolved solids. The total suspended solid, total solid, dissolved oxygen, biochemical oxygen demand (BOD), Chemical oxygen demand (COD), sulphide and chloride were found to be higher than the specified 51 limit (WHO, 1984). The colour of the waste water at 'A' was brown, at 'B' was dark brown and treated effluent was light brown (Table 5) . All the three effluents were fo\and deficient in dissolved oxygen. Dissolved oxygen in water is necessary to sustain many forms of aquatic llfe^ The low solubility of oxygen induced by temperature, total solids and organic matter could lead to such low dissolved oxygen level that the aquatic organism could not survive. The pH at 'B* was also found to be highly alkaline, i.e., 10.5. This is due to the presence of sodium hydroxide which comes from mechanical and cold caustic soda pulp plant. The maximvun turbidity at 'B'i.e., 75 NTU, which also affected the turbidity of the water. The turbidity is an aesthetic problem for domestic waters but it can also be significant for irrigation because solid particles can settle down and clog the water distribution system (Mutlak, et al., 1980). All the samples contained large amounts of solids. Sulphide was present in high concentration in all the three samples ('A', 420.8 mgl" ; 'B', 552.0 mgl"^; treated effluent 371.2 mgl" ), High sulphide concen tration might be due to the different types of raw materials employed. 52 The presence of very high concentration of chloride ('A', 1005 mgl" ; 'B', 920 mgl" ; "C 900 mgl ), might be largely contributed by bleaching process. The COD and BOD values were found to be very high (COD values of sample 'A', 740 mgl" ; 'B', 1716 mgl" ; 'C', 300 mgl" ) (BOD values, 'A*, 185 mgl" ; •B', 622.5 mgl"^; 'C' 48.5 mgl"'^) . These high values of COD and BOD are due to the presence of large amount of organics and inorganic sulphides etc. Hamxjunanula, V. and Subrahmanyam p.v.R. (1976) found that the main polluting constituents in combined waste water are suspended solids, colour, foam/ inorganic sulphides, toxic chemicals (mercaptans), BOD and COD. It is therefore, not desirable to discharge untreated pulp and paper mill waste into surface water. Heavy metals such as Fe, Mg, Cu, Zn, Mn, Ni, Cr and Cd were found within the permissible limits (Table 6) except lead which was present in high concen tration in all the three samples ('A', 0.683 mgl" ; 'B', 0.909 mgl" and 'C, 0.658 mgl" ). Hg was detected in the samples 'A' (0.018 mgl" ) and 'B') (0.065 mgl" ), but it was not detected in the treated waste water which is due to the effectiveness of the mercury recovery plant. 53 The iintreated wastes — A and B — are therefore highly objectionable for discharging into surface water. Although the waste water after treatment is discharged into surface water but due to high concen tration of toxic metals like Pb it is not desirable for discharging it into surface water as it is harmful for the aquatic life. Foamy material discharged from the factory has direct toxic action on the aquatic organisms and this also hampers reaeration processes (Gurd, 1956). Elaborate treatment facilities need to be ]f>rovided. Recently the treated waste water are being dis charged on land for irrigation purpose (IS-3307-1965), Bhalerao/ B,B. and Alagarswamy {197J8)/found that disposal of waste water on land for irrigation after fulfilling ISI standard can lead to pollution control and land irrigation. It is a common practice in advanced countries to treat industrial waste waters with municipal waste water in a combined treatment plant to maintain desired quality of final effluent all the time. The industrial waste will be easier to treat since it will be equalised, diluted and partially neutralized by the domestic sewage. There will be savings in treatment and capital costs and the space if available in the 54 factory premises, can be used for factory expansion rather than waste treatment. A similar approach in India is desirable in case of combined treatment of pulp and paper mill waste water and municipal waste water. Due to the lack of adequate nutrients such as nitrogen and phosphorous which are readily available with municipal waste water, biological treatment is easier and will be effective in reducing the suspended solids and BOD. The use of process water, efficient chemical recovery and reuse can minimise the organic load and quality of waste water. I -.I'M'f " I T'l ill. i-.ir\r f ( III •-.1/-1,11 I IP i--.r :;:i •«•': r i-« 1^11 L... I— s L... • I • !.:> _ , I •• •«J ^ » " ii" •I' • '•••' 1" -»" -^ *'""" '^ PROCESS FLOW CHART CHEMICAL PULPING PLAMT BAMBOO CHIPPER DIGESTER WASHER SCREENING HOUSE e.L. B.L. TO CHEMICAU J RECOVERY UNIT TO STOCK FINAL PULP BLEACHING •DECKER PREPARATION STORAGE SEcflON TO E-T. P. p-\rr COLD BODft ruLPiNt; PLnrji BAMBOO STORAGE SCREW DIGESTER -»— REFINER WASHER CHIPS TANK PRESS \ B.L. BL. > lOCHEMICAL RECOVERY UNIT FINAL TO STOCK >• —<- PULP HASHER REFINING BLEACHING THICkNER SCRttNIHG PREPARATION STORA6E UNIT -t^>- TO E.T. P. GROUND WOOD PULPINO PL AN I ( MECHANICAL PULPING ) SALAI COWAN DECKER FINAL PULP TO STOCK GRINDER SC^EENIMG UlASHIMG PREPARATION UlOOP SCREEN THICkNER UNIT TO E.T. R ^ o i-t t.: m g n i; fl Ul >" -* u: (ji •< fj a: ^'^ H- 2 Z III cr a a. , < < ID Ul ^ UJ •f ^a- u 1 0 < (U . CL 0 LU • ( Z 1— (/I Q »— z *3 < Ul _J Ui 1/1 u H u. - - — CO _J (— a 1., 2 2: ^ Ul 0 - -„ — if 1 LU •4 2 0 a. !< _J LU z P ^ 0 a 2 *fl 1— 1— »— H- _J 2: 0 yz 1 1 Q. 1 • 1 tr 3 2. Q. _j !S> ii. z 5 u. c LU 3 .2LU: Q III _j ir < Ul Z 0 0 < < r 10 cn iris 56 B ^ • in M O O O o B 10 a> +> n B At a» o o o O in O in O O o 3E • U • • • • • • »:) * » • • m ^ ca >* 00 «» tn o o H CN vO CM CO H Z CM rH H •«J" m o\ a\•* (oM r- 0o\ vO in H (0 u Q « 0. (d -u Oi C 1 0) 0. E H •> 0 (0 XO o.g o o o o o 00 o o o o O in «4-l t^ • ^a • • • • 1 • ij • * • • 0 o CO 00 in ro o H in o CM o 0) M m\o 5 H t^ t^ CM • o 00 <* VO in H n 0) CuO ^ n in 00 00 z r-i p' •<* CM •8 0 +J CM M 4J «C CO •H +) U C 0) 0) +J 3 0 -H (d U4 U «M 10 U JS fO u O rH (0 u < -uH O (0 E ^*K J J O uV) 0) in E2* (0 < CM x: >i y*K o» (0 0) c V o 6 -0 -0 ^i^ +J (U •P 0 )o >•• •H •H D (0 o» •H 0] 0 s.-^ H H >^ B n •H m (0 0 0 g X •H 4) V.o' s Jl^^ n T3 (0 m U 0 ^"s ^ B >i s •rC \ »J 10 -0 0) H -0 T3 >i 0) •0 \ \a AJ U x04: 4sJ 0 0) Q) •P O H r0 10 CO -0 > •H <>u w 2* (0 J: M U B H H v_,E^ N-ig' « d rH 0) 0 -•aH g^^ 0 r-i iH •p Oi 0 10 a X) 0] in (0 (0 g H •P 0a) (0 M n Q Q •P -P 0) 0 0 3 •H 3 K U •H o O 0 0 H U EH (0 Q EH D« U Q CQ U EH H u 57 o •* in in O o o a\ o O o\ m o O CM O o en in U o ON >-i o 0\ ro H O lf> H in a\ CM o 00 "* M o CM o m P* in CM * iH ON ro c 0) > •H 0» a> 03 VO CM CM o o u o O CO O o H *0 O o o n • • • • • • • • • • » O (0 o CO 00 o ON ^ iH o o CM cn CO 3 o o u •ap cu (U (0 0) u u Id •H n 0) o c CO c n o u u 0) (U (V •P 0) u V 0) 0) Id in n 0) Id •p (0 n u •H a Id 0) u o c (t) o 0. M-l •H Q, H <0 H H H o en CM (d (0 ON o o iH IT) JC x: o o U o (0 CO w !Z Z o u CO 58 Table 6 Concentration of Heavy Metal in the Pulp-Paper Mill Waste and Effluent After Treatment (mgl"-'-) SAMPLING SITE Elements A 6 C Pe 43. ,08 21. .44 13. .88 Mn 6. .56 1. .32 0. .073 Ni 0. ,115 0. ,298 0. ,133 Cu 0. .035 0. .258 0. .057 Pb 0, .683 0, .909 0. ,658 zn 0, ,090 0. ,118 0, ,036 Cr 0. ,640 0. .950 0, .813 Cd 0. ,010 0. .023 0. ,007 Hg 0.018 0.065 ND ND = Not determined Chapter IV PHYSICO-CHEMICAL STUDIES ON GANGA WATER (INDIA) Introduction The rapid advances in chemical technology have led to the increasing use of new organic and inorganic chemicals as the raw materials in different industries. This has resulted in the discharge of large quantities of these materials through industrial and domestic wastes. These effluents add a larger amount of non- bio-degradable materials as well as toxic metals to the biota of the receiving streams, Abdullah and Royle (1972* 1974a) have reported the presence of metals (Cu, Zn, Mn* Fe, Pb, Cd and Ni) in the waters of Welsh rivers and lakes, Hantge (197fi) has studied the pollution of Nahe river and its tri butaries in Germany and showed that high pollution levels at certain points were due to pouring of domestic and industrial waste into it, Takabayashi et al.(1980) analysed the waters of the upper Amazon river physico- chemically and found it strongly acidic throughout the stretch of the river mainly due to humic acid. Ajmal et al.(1982) have shown that the Ganga river is highly 59 60 polluted at Kanpur, Allahabad and Varanasi due to the indiscriminate discharge of industrial and sewage effluent into it. They have also found that coal-fired thermal power plant is responsible for the elevation of metallic contents in the water and sediments of Upper Ganga Canal (Ajmal et al., 1983a, 1983b). Mathur (1987) studied the metal pollution in river Ganga at Varanasi. Bhargava (1984, 1985) and Singh (1985) studied the water quality of Ganga river and reported that it is unsuitable for use as drinking water and for bathing in all urban centres and undergoes significant changes due to seasonal effect. Kuo (1986) studied the water quality of the major and minor rivers in Taiwan. Cabrera et al. (1987) studied the degree of heavy metal pollution of the Guadiamar river and the Guadalquivir estuary in Spain. Suzuki et al. (1987) reported the trace metal concentration in the Tama river, Japan. The amount of trace metal are almost the same throughout the entire drainage system. Nakamura (1985) has studied the river water pollution in Izuhara-Cho, Nagasaki Prefectures, Japan from 1983 to 1985. Venkateshwarlu (1986) analysed the physical, chemical and algal parameters at both unpolluted and polluted sites in 61 Godavari river in Andhra Pradesh, India. Ganga, one of the most significant rivers of India, after originating from Gangotri in the Himalayas, tra verses 2,525 km before it joins the sea in the Bay of Bengal. The social, cultural and industrial activities along the banks of the river have damaged the quality of the Ganga water, and the use of polluted water has created a potential danger to aquatic life and human health. This chapter deals with our studies on the seasonal variations in the physico-chemical parameters and heavy metal contents of Ganga river water from October 1987 to June 1988 from Narora to Kannauj (Fig. 2). Pour sampling stations as described in Table 7 were selected for periodic monitoring. Samples will be collected once in different seasons — post-monsoon (September-October) , Winter (December-January) , Spring (March-April) , and Summer (May-June) . RESULTS AND DISCUSSION The physico-chemical characteristics of the water of Ganga river collected from various sampling stations have been given in Table 8. The results show that the pH values of Ganga water at different sampling stations have been found to be well within the admissible value of 6.0 to 9.0 (IS 229:1982). The river exhibited an alkaline range of pH 7.8 - 8.8 62 Ganga has been found to be moderately warm. The maxlmvun temperature recorded was 33 c at KannauJ during sxuraner (Table 8 ) . The water temperature varies between 21-30°C. The mlnlmxim temperature recorded was 14.8 c at Fatehgarh during winter. The turbidity gradually Increases from Narora (14.0 MTU) to the highest level (41.0 NTU) at KannauJ during post-monsoon period. This Is most probably due to high turbulence and heavy soil erosion after the monsoon. There Is a gradual Increase in the electrical conductivity from Narora to Kannauj (360 Aimhos/cm to 410.0 ;umhos/cm) .during spring whereas this pattern is not found in the other seasons namely summer, winter and post-monsoon (Table 8) . The concentration of the total dissolved solid (TDS) indicating presence of various dissolved salts rapidly rises from Narora to Kannauj but is lowest in summer period as compared to the other seasons with tlie exception of Narora (137 mg 1~ ) (Table 8) . Variations in the concentration of TDS from one station to another depends largely upon the availability of sewage and industrial effluents to the receiving stream. It has also been observed that as the river 63 travels downstream at Kannauj the TDS concentration increases with the exception of svuraner season. The alkalinity status of the Ganga water is shown in Table 8, The alkalinity increases from Narora to Kannauj in post-monsoon and winter season. The chloride concentration (Table 8 ) at Narora in Spring is found to be 6.0 mgl" which rises upto 13.0 mgl" in Kannauj. The range of chloride concen tration has been found to range from 5.0 to 13.0 mgl" , The seasonal variations of the chloride content are virtually absent. Klien (1957) found a direct correla tion between chloride concentration and pollution level. The presence of higher value of chloride in the river showed higher pollution load. The sulphate concentration in summer range from 10 mgl" at Kachchla to 17.8 mgl" at Narora (Table 8) . The concentration of sulphate remained the same in summer at Fatehgarh and Kannauj (16.0 mgl" ). This suggests that flushing of these ions into the river from surface runoff occurs during spring rains and decreases during dry period as was also observed by Qadri et al. (1981). The range of sodium concentration (Table 8) rises from 3.0 mg/1 at Narora to 14.0 mgl" at 64 Xannauj in post-monsoon. The same trend has also been found in winter. The maximum concentration was found at Kannauj (17«0 mgl" ) during winter. The calcium concentration is not seen to vary much during the winter and stunmer (Table 8 ) . It increases from Narora (32,9 mgl" ) to Kannauj (42.1 mgl" ) during winter. Increased hardness during winter and spring is a result of poor dilution in water due to low precipitation. Considerably high rain fall in monsoon dilutes the water and reduces the bicarbonate percentage. The total Kjeldahl's nitrogen (ammonical + organic) is an important indicator of pollution. It arises from the anaerobic decomposition of nitrogenous matter present in the stream (Klein, 1957). It has been found to rise from Narora to Kannauj during post- monsoon (Table 8 ) . The highest concentration of ammonia nitrogen was observed (3.7 mgl" ) at Fatehgarh during spring. High concentration of nitrogen is not desirable as it is harmful to fish (IS : 229-1982; 1.2 mgl"-"-) . Phosphate-phosphorous is one of the most important limiting nutrients. The range of phosphate-phosphorus in winter lies between 3.02 mgl" (Kachchla and Fatehgarh) and 3.62 mgl" (Narora and Kannauj)(Table 8 ). These 65 studies have shown that the concentration of PO_-P 4 at Narora is almost the same in all seasons. The high phosphate concentrations in the river water may be due to the cremation of bodies at the river banks. Organo-phosphorus pesticides and phosphate fertilizers which are in extensive use these days, ultimately reach the river by surface runoff, causing the increase of the PO -Phosphorus in the river. The dissolved oxygen (DO) exhibits a more or less stable pattern in the Ganga water (Table 8 ). The DO level is the highest in winter, somewhat lower in the post-monsoon period, and is the lowest in the summer. A few exceptions are noticed at some stations. The lowest value is 5.2 mgl" at Narora during post- monsoon and highest value is 9.53 mgl~ at Fatehgarh in the winter season. The most redeeming feature of the Ganga water quality is that the DO level is usually higher than the minimum limits required for support of fish fauna (4.0 mgl" ) and as a source of drinking water (4.0 mgl" )(is: 229-1982). The biochemical oxygen demand (BOD) and chemical oxygen demand (COD) tend to increase from 4.9 mgl" to 10.5 mgl" ; 12.2-25.5 mgl" at Narora and Kannauj during winter. The BOD and COD concentrations are 66 significantly high along the Kannauj stretch and are low at Narora (Table 8 ). Seasonal variations have not been found in BOD and COD values. The point of great concern is the fact that the BOD level has been found to be higher than the permissible limit (3 mgl" ) (IS: 229-1982) throughout the dry period from Narora to Kannauj. The water^ therefore^ cannot be used for domestic purposes without conventional treatment and disinfection. The concentration of heavy metals (Cd, Cu, Mn, Ni, Hg and Zn) in river water at different sampling stations have been presented in Tables 9. The presence of various metals in the aquatic environment is dependent on a wide range of chemical, biological and environmental factors. Among them the important factor which influences the availability of trace metals in the aquatic system is the hydrogen ion concentration (pH). The pH of the whole stretch of the river monitored was in the range of 7.8-8.8. The effect of pH changes on the speciation of zinc, copper, cadmium and lead was computed by Zirino and Yamamoto (1972). The free ions are found mainly at low pH, whereas the metals get precipitated at higher pH values. Metzner (1977) studied the fate of copper, lead and zinc at different pH values in wastewater 67 and found that solubility of the metals is optimum at pH 7 and decreases with the increase in pH upto certain values. The trend has been observed in Fatehgarh samples (Table 9 ) . This behaviour of these metals due to entering of the pollutants from diverse non-point sources into the river. The world's mean stream concentration of copper as reported by Goldberg et al. (1971) was 7 Aigl" , whereas in the Ganges river it was found as high as 47.70 MQ^~ at Kannauj. It was due to the fact that river contained high suspended solids. Probably adsorbed trace metals on the suspended matter were responsible for these high values as they were analyzed in the term of total metal content in the system. Narora has a big reservoir of water for irrigation purposes in the shape of a dam from where three canals emerge. It is presumed that high metallic contents are being dumped into the reservoir resulting in higher metallic levels at Narora (Ajmal et alw 1984) . Cadmium in the water was found to vary in the range of 1.8 Aigl" - 11.8 wgl" . However, the maximum concentrations of cadmium vvas determined in the river water at Fatehgarh (Table 9 ) which was above the permissible limit (0.005 mg/1, WHO, 1984:). The highest zinc concentration was found at 68 Kannauj (217.0 Aigl" ) are more than ten times of the world's mean stream concentration of zinc (20 ;agl~ ) (Goldberg, 1971). Manganese levels were highest in the water samples collected from Kannauj (40.10 Aigl" ) . The manganese concentration at all different stations has been found within the permissible limit (100 /ugl~ , WHO, 198i). Nickel is found mostly in summer season. The highest concentration was found in Kannauj (99,5 Aigl" ) and could not be detected in Narora (Table 9 ). Mercury level has been found to be above the per missible limit d.O^gl" , WHO, 1984). The highest value was found at Kachchla (22.0 Mgl~ ) and the lowest in Narora (2.2 wgl" )(Table 9 ) due to indus trial effluent and geological weathering. The river has been found to be highly polluted at Kannauj and moderately at Fatehgarh, Kachchla and Narora. The self purification character of the river is appreciable. The level of cadmium in the Ganga river has been found to be very high and are much more than the permissible limits. 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