Final Final Final

Groundwater Analysis … 2010

ACKNOWLEGMENTS

I heartily like to dedicate this thesis to my Parents.

This journey had never been possible without all colleagues, friends and family that have supported me during this year.

First of all I would like to thank my guide Ms. Sonal Verma for her support and clear view as well I am very grateful to my co-guide Mr Mihir R. Vyas for all the support and freedom to explore during this journey and for always taking time for me whenever I needed direction and guidance. I would also like to thank all the staff of TIFAC CORE for their support and help whenever needed.

Huge thanks to my colleagues, for excellent company and help during research. It’s here impossible to mention everyone and I would probably still forget someone but you know who you are. You have all been fantastic. I would like to thanks everyone involved here for paving the way to this thesis.

My all friends outside of TIFAC CORE all deserve thanks for providing well needed distraction and friendship.

Lastly I would like to thanks my family and the God who made me this much capable.

Purohit Hitesh B.

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Study on Groundwater quality of Selected Area of Surat City and Removal of Phenol by Rice Husk and Rice Husk

Ash in Aqueous Systems.

Abstract: Ground water samples were collected from different locations around Surat city, Gujarat (India). These water samples from 10 sampling points of surat city were analyzed for their physicochemical characteristics. Laboratory tests were performed for the analysis of samples for pH, Electric conductance, Fluoride, Hardness, Alkalinity and Phenols etc. On comparing the results against drinking water quality standards laid by CPCB it is found that all of the water samples are non-potable for human being due to high concentration of one or the other parameter. The potential of rice husk and rice husk ash for phenol adsorption from aqueous solution was studied. Adsorption studies were carried out under varying experimental conditions of pH, phenol concentration and adsorbent dose. Adsorption of rice husk and rice husk ash was achieved within 3 hr for various phenolic concentration 0.2-1.0 mg/100ml, various pH 5 to 11 and Adsorbent dosage varied from 1g to 4g and 0.1g to 0.4g for Rice husk and its ash, respectively for phenol concentration 1 mg/100ml. The sorption capacity was decreased with an increase in the pH and an increase in the initial phenol concentration. A comparative study showed that rice husk ash is very effective than rice husk for phenol removal. The studies showed that the rice husk ash can be used as an efficient adsorbent material for removal of phenolic from water and wastewater.

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CONTENTS

CHAPTER P.N.

1: INTRODUCTION 5

1.1 Water cycle 6

1.2 Definition 7

1.3 Groundwater movement 9

1.4 Groundwater storage 9

1.5 Groundwater uses 11

1.6 Groundwater contamination 11

1.7 Removal of pollutants by soil 13

1.8 pH, EC, Fluoride, Hardness, Alkalinity and Phenol 14

1.9 Activated carbon adsorption 18

2: OBJECTIVES AND SCOPE OF STUDY 20

3: LITRATURE REVIEW OF THE STUDY 223.1 Phenol contamination

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Case study 1

Case study 2

3.2 Adsorption study 24

Case study 1

Case study 2

Case study 3

Case study 4

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4: METHODOLOGY OF STUDY 30

4.1 sampling locations 31

4.2 Methods for Analysis of Groundwater 33

5: RESULT AND DISCUSSION 41

5.1 Groundwater Analysis 42

5.2 Proximate Analysis 48

5.3 Adsorption study of RH and RHA 49

CONCLUSIONS 53 REFERENCES 54

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CHAPTER – 1

INTRODUCTION

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INTRODUCTION

When people think of a water source, they think of lakes, rivers and streams; in other words, surface water. However, of all of the usable freshwater in the world, approximately 97 percent of it is groundwater. According to the United Nations, 10 million cubic kilometres of water are stored underground. The United States Geological Survey states that there is about 4.2 million cubic kilometres of water within 0.8 kilometre of the earth’s surface. Environment Canada cites a study that estimates that all of the groundwater in the world would cover the surface of the earth to a depth of 120 metres, while all of the surface freshwater would only cover the earth to a depth of 0.25 metre! While groundwater estimates can vary, scientists agree that there is a lot of water under the earth’s surface!

1.1What is the Water Cycle?

Water can be found on Earth in three different states liquid, solid, and vapor. Not only does water cover three fourths of the Earth's surface, but it also flows underground, and floats in the air. The following percentages show the water distribution on Earth:

Ocean 97.2%Ice Caps/Glaciers 2.14%Groundwater to depth of 13,000 ft. 0.61%Fresh Water Lakes 0.009% Inland Seas/Salt Lakes 0.008%Soil & Subsoil Moisture 0.005%Atmosphere 0.001%Rivers 0.0001%Biota (within living plants, animals, & humans)

0.0001%

When precipitation falls to the Earth, some part of it may be intercepted by trees, vegetation, and buildings. During brief or light storms, this intercepted water usually evaporates rapidly and is known as interception loss. During longer and heavier storms, water does reach the ground and can follow many different paths as the diagram shows.

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Water can pool on the surface and evaporate, infiltrate the ground, or become surface runoff. If the water infiltrates the ground it can become interflow, be taken up by plant roots, or recharge the groundwater and become baseflow. Interflow is water moving laterally or horizontally in the zone of aeration during and immediately after storms. This water discharges directly into a stream or lake.

Vegetation that is actively growing during the summer absorbs the water as it infiltrates the ground, so not much water reaches the zone of saturation. However, when vegetation is growing at a slower rate, more water will recharge the groundwater. The major periods for recharge of the aquifer occur in the spring and fall when precipitation is usually greater and plant growth is slower.

Precipitation that falls at a fast rate may not be absorbed by the soil, so it becomes surface runoff. Surface runoff can take many forms such as overland flow, or saturation excess overland flow.

1.2What is Groundwater? Groundwater is water that accumulates underground. It can exist in spaces between loose particles of dirt and rock, or in cracks and crevices in rocks. Different types of rocks and dirt can contain different amounts of water. The saturation zone is the portion of the soil and rock

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that is saturated with water, while the unsaturated zone is the portion of the soil and rock that is not saturated. The top of the saturated zone is called the water table. The diagram below illustrates these terms.

When it rains, the water infiltrates the soil and percolates downwards until it reaches the water table. Some types of soils allow more water to infiltrate than others. Permeable surfaces, such as sand and gravel, allow up to 50 percent of precipitation to enter the soil. Rainwater can take years or even decades to reach the water table. Due to the immense volume of groundwater, once rainwater reaches the water table, it often remains there for an extremely long period of time. Some water that is currently stored in the ground may be rain that fell hundreds or thousands of years ago.

Aquifers are underground layers of permeable rock, gravel, sand or clay that water can be extracted from. From the above diagram, you can see that different types of rocks and soils can hold different amounts of water, depending on the porous areas (or spaces). When the spaces are large enough to contain usable quantities of water, it is called an aquifer. Large particles, such as coarse sand and gravel, can hold more water than fine sand and clay, because the spaces between gravel particles are larger than the spaces

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between fine sand particles. So, we can say that gravel has a greater porosity, or ability to hold water, than clay.

1.3 How Does Groundwater Move?

Groundwater moves from areas of higher elevation to areas of lower elevation or pressure. This is where the groundwater is released into streams, lakes, wetlands, or springs. The baseflow of streams and rivers, which is the sustained flow between storm events, is provided by groundwater.

1.4 Groundwater Storage in Aquifers

Groundwater is stored in subsurface void spaces below the water table. The geologic material that stores, transmits, and yields groundwater to wells and springs is called an aquifer. To be an aquifer, it must store and transmit water at rates fast enough to supply reasonable amounts to wells and springs. Therefore, not all groundwater is stored in an aquifer. Productive aquifers can be comprised of sand and gravel, sandstone, limestone and dolomite.

Three main types of aquifers exist:

Unconfined aquifer Confined aquifer

Perched aquifer

Unconfined Aquifer

An unconfined aquifer has no confining layers between the zone of saturation and the land surface.

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Confined Aquifer

A confined aquifer is overlain by a confining layer or aquitard, which is geologic material with little or no permeability/hydraulic conductivity. This layer does not allow water to pass through or the rate of movement is extremely slow. Often clays and silts, or rocks such as shale comprise confining layers. If the potentiometric surface is above the land surface, then a flowing artesian well or spring may occur.

Perched Aquifer:

A perched aquifer is a saturated zone within the zone of aeration that overlies a confining layer. A perched aquifer sits above the main water table.

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1.5 Groundwater uses:

Irrigate the crops, Nourish fragile ecosystems such as wetlands and feed rivers, streams and lakes, Clean our bodies, clothes, and homes Supplement our recreational activities And, most importantly, to hydrate our bodies. 1.5 billion people worldwide depend on groundwater for drinking water.Of the world’s water that is usable by humans, 98% is stored in aquifers as groundwater.

1.6

Groundwater contamination

Groundwater can become contaminated by many of the same pollutants that contaminate surface water. Pollution of groundwater occurs when contaminants are discharged to, deposited on, or leached from the land surface above the groundwater. Even if there are no industrial or domestic pollution sources in the area, it is important to realize that the water may not be free from contaminants and should be tested before human consumption.

(1) Natural Sources

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Groundwater contamination can occur in many ways and from many sources, both natural- and human-induced. Groundwater commonly contains one or more naturally occurring chemicals, leached from soil or rocks by percolating water, in concentrations that exceed federal or state drinking water standards or otherwise impair its use. Dissolved Solids and Chloride, Iron and Manganese, Nitrate-Nitrogen.

(2) Human Activities

Contaminants can enter groundwater from more than 30 different generic sources related to human activities. These sources commonly are referred to as either point or nonpoint sources. Point sources are localized in areas of an acre or less, whereas nonpoint sources are dispersed over broad areas.

The most common sources of human-induced groundwater contamination can be grouped into four categories:

a) waste disposal practices b) storage and handling of materials and wastes

c) agricultural activities

d) saline water intrusion.

a) Waste Disposal Practices

Waste disposal can take a number of forms septic systems, municipal and industrial landfills, surface impoundments, waste-injection wells and direct application of stabilized wastes to the land. In addition to these regulated forms of disposal, a considerable amount of unregulated disposal, such as illegal dumping and accidental spills, contributes to groundwater contamination.

b) Storage and Handling of materials and wastes

Groundwater contamination as the result of storage and handling of materials includes leaks from both above-ground and underground storage tanks, as well as unintentional spills or poor housekeeping practices in the handling and transferring of materials on industrial and commercial sites, Leaking Underground Storage Tanks, Transporting and Stockpiling, Mining Practices, Oil-Well Brines etc.

c) Agricultural activities

Agriculture is one of the most widespread human activities that affect the quality of groundwater agricultural activities include use of fertilizers, pesticides, feedlots and irrigation activities which may cause contamination of groundwater.

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d) Saline Water Intrusion

Areas surrounded by the saltwater need to be concerned about contamination by sea water. Since the specific gravity of fresh water is less than that of salt water, fresh water floats on top of sea water, forming a fresh water lens.

2 Removal of pollutants by soil from the water before it reaches the aquifer.

In many cases, the soil can remove bacteria, viruses and chemicals from water that percolates downward. After all, that is one way in which nature cleans water. But not all soils remove contaminants as effectively as others, and domestic and industrial waste can also exceed the soil’s ability to remove chemicals and contaminants. Some soils allow water to quickly percolate down to the aquifer. This generally means that less of the contaminants will be removed. As well, when the pollutants originate from an underground source, such as a storage tank or septic system, they may be very close to the groundwater and the soil does not have enough time to remove all harmful substances. The quality of the groundwater depends on the temperature, the pressure (which depends on how deep the groundwater is), the type of rock and soil and the residence time of the water.

Groundwater moves very slowly, generally between a few millimeters and a few meters each day. This means that contamination tends to be concentrated and localized, close to the pollution source. However, contamination can spread within the aquifer, or to nearby lakes and streams. Often, groundwater pollution is not noticed until the water is already contaminated and an expensive remediation process is required. It is extremely expensive and difficult to reverse groundwater contamination, and it may take decades before the water is usable again.

If we compare an organic pollutant in groundwater to one in surface water, groundwater has fewer microbes to digest organic pollutants, less oxygen no sunlight and surface from which organic pollutant can evaporate. Chemical structures most susceptible to oxidation include phenols, aromatic amines, and dienes. Saturated alkyl compounds such as alkenes, halogenated alkenes, alcohols, esters, and ketones may not be significantly oxidizable in the groundwater environment. Especially in slow moving groundwater, pollutants can persist indefinitely.

Majorly rural areas in Surat city are located near GIDCs and industrial area. Groundwater consumption in rural areas is higher than in urban area, people in urban area use Municipal water for their domestic and drinking purpose while People in rural areas use groundwater generally for their drinking, domestic and Agricultural purposes. So the groundwater analysis is necessary for the healthy development of man, animals and plants. Surat city is largely recognize for its Textile business. Phenols are common Toxic organic pollutants from Textile industries. It evaporates more slowly than water and dissolves fairly well in water and can

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easily perforate into Groundwater. So the chances of Groundwater contamination by Phenols may be high near industrial areas.

Determination of water quality parameter viz- pH, Electrical Conductance (EC), Total Hardness, Total Alkalinity, Fluoride and Phenols is necessary for the suitability of Groundwater for drinking purpose & healthy development of man, animals and plants.

1.8 (a) pH:

Ground water, especially if the water is acidic, in many places contains excessive amounts of iron. Iron causes reddish stains on plumbing fixtures and clothing. Like hardness, excessive iron content can be reduced by treatment. A test of the acidity of water is pH, which is a measure of the hydrogen-ion concentration. The pH scale ranges from 0 to 14. A pH of 7 indicates neutral water; greater than 7, the water is basic; less than 7, it is acidic. A one unit change in pH represents a 10-fold difference in hydrogen-ion concentration. For example, water with a pH of 6 has 10 times more hydrogen-ions than water with a pH of 7. Water that is basic can form scale; acidic water can corrode. According to U.S. Environmental Protection Agency criteria, water for domestic use should have a pH between 5.5 and 9.

(b) Ec (Electric conductivity):

Conductivity of a substance is defined as 'the ability or power to conduct or transmit heat, electricity, or sound'. Its units are Siemens per meter [S/m] in SI unit.

An electrical current results from the motion of electrically charged particles in response to forces that act on them from an applied electric field. Within most solid materials a current arise from the flow of electrons, which is called electronic conduction. In all conductors, semiconductors, and many insulated materials only electronic conduction exists, and the electrical conductivity is strongly dependant on the number of electrons available to participate to the conduction process. Most metals are extremely good conductors of electricity, because of the large number of free electrons that can be excited in an empty and available energy state. In water and ionic materials or fluids a net motion of charged ions can occur. This phenomenon produces an electric current and is called ionic conduction.

Pure water is not a good conductor of electricity. Because the electrical current is transported by the ions in solution, the conductivity increases as the concentration of ions increases.

Conductivity in groundwater occur by some cations like sodium, calcium, magnesium, potassium, iron and strontium and anions like bicarbonate, sulfate, chloride, silica, carbonate, nitrate, fluoride, boron

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Typical conductivity of waters:Ultra pure water 5.5 × 10-6 S/mDrinking water 0.005 – 0.05 S/mSea water 5 S/m

(c) FLUORIDE:

Most of the fluoride found in groundwater is naturally occurring from the breakdown of rocks and soils or weathering and deposition of atmospheric volcanic particles. Fluoride can also come from, Runoff and infiltration of chemical fertilizers in agricultural areas, Septic and sewage treatment system discharges in communities with fluoridated water supplies Liquid waste from industrial sources etc.

Environmental health concerns of Fluoride:

At low concentrations fluoride can reduce the risk of dental cavities. Exposure to somewhat higher amounts of fluoride can cause dental fluorosis. In its mildest form this results in discolouration of teeth, while severe dental fluorosis includes pitting and alteration of tooth enamel. Even higher intakes of fluoride taken over a long period of time can result in changes to bone, a condition known as skeletal fluorosis. This can cause joint pain, restriction of mobility, and possibly increase the risk of some bone fractures.

(d) TOTAL HARDNESS:

Water hardness is primarily the amount of calcium and magnesium, and to a lesser extent, iron in the water. Water hardness is measured by adding up the concentrations of calcium, magnesium and converting this value to an equivalent concentration of calcium carbonate (CaCO3) in milligrams per litre (mg/L) of water.

Sources of water Hardness:

Water hardness in most groundwater is naturally occurring from weathering of limestone, sedimentary rock and calcium bearing minerals. Hardness can also occur locally in groundwater from chemical and mining industry effluent or excessive application of lime to the soil in agricultural areas.

Environmental health concerns of Hardness:

Hard water is mainly an aesthetic concern because of the unpleasant taste that a high concentration of calcium and other ions give to water. It also reduces the ability of soap

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to produce a lather, and causes scale formation in pipes and on plumbing fixtures. Soft water can cause pipe corrosion and may increase the solubility of heavy metals such as copper, zinc, lead and cadmium in water. In some agricultural areas where lime and fertilizers are applied to the land, excessive hardness may indicate the presence of other chemicals such as nitrate.

Hardness rating Concentration of calcium carbonate (mg/l)

Soft 0 to < 75

Medium 75 to < 150

Hard 150 to < 300

Very hard Greater than 300

(e) ALKALINITY:

Alkalinity refers to the capability of water to neutralize acid. Alkalinity expresses buffering capacity of groundwater. A buffer is a solution to which an acid can be added without changing the concentration of available H+ ions or without changing the pH appreciably. It protects the water body from fluctuations in pH. Alkalinity is often related to hardness because the main source of alkalinity is usually from limestone. Which are mostly CaCO3. Hard water contains metal carbonates (mostly CaCO3), it is high in alkalinity. Soft water usually has low alkalinity and little buffering capacity. So, generally, soft water is much more susceptible to fluctuations in pH from acid rains or acid contamination.

Effects of Alkalinity on Environment and Human Health:

Alkalinity is important for fish and aquatic life because it protects or buffers against rapid pH changes. Living organisms, especially aquatic life, function best in a pH range of 6.0 to 9.0. Alkalinity is a measure of how much acid can be added to a liquid without causing a large change in pH. Higher alkalinity levels in surface waters will buffer acid rain and other acid wastes and prevent pH changes that are harmful to aquatic life.

(f) PHENOLS:

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Phenol, also known as carbolic acid, is an organic compound with the chemical formula C6H5OH. It is a white, crystalline solid. This functional group consists of a phenyl, bonded to a hydroxyl (-OH). It is produced on a large scale as a precursor to many materials and useful compounds. Phenol is appreciably soluble in water. It is a mildly acidic compound that requires careful handling.

Sources of Phenols:

Phenol is obtained from coal tar and is widely used as a disinfectant for industrial and medical applications. It also serves as a chemical intermediate for manufacture of nylon-6 and other man-made fibers and for manufacture of epoxy and other phenolic resins it is also use in textile dyeing and as a solvent for petroleum refining.

Effects of Phenols on Human Health: After ingestion phenol produces burning pain and white necrotic lesions in the mouth, oesophagus and stomach, vomiting and bloody diarrhoea. After skin exposure, pain is followed by numbness and the skin becomes blanched. The systemic clinical effects of phenol are independent on the route of exposure, they include: headache, dizziness, hypotension, ventricular arrhythmia, shallow respiration, cyanosis, pallor; excitation and convulsions may occur initially, but it is quickly followed by unconsciousness. A fall in body temperature and pulmonary oedema may occur. Methemoglobinemia and hemolytic anemia have been reported occasionally. The most important effects in short-term animal studies are neurotoxicity, liver and kidney damage and respiratory effects. The available data do not suggest a strong potential for cumulative health effects from chronic exposure.

1.9 Activated Carbon adsorption

Activated carbon, also called activated charcoal or activated coal is a form of carbon that has been processed to make it extremely porous and thus to have a very large surface area available for adsorption. Activated carbon is carbon produced from carbonaceous source materials like nutshells, peat, wood, coir, lignite, coal and petroleum pitch.

I have used Rice Husk & Rice Husk Ash for the removal of Toxic organic pollutant phenol because Rice husk is cheap and it is available in large source, it is use in villages to feed their cattle and to making their huts.

Examples from active carbon in different processes:

Ground water purification, de-chlorination of process water, Water purification for swimming pools, polishing of treated effluent

For Adsorption of organic, non-polar substances such as:

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Mineral oil, BTEX , Poly aromatic hydrocarbons (PACs), Chloride, phenol Adsorption of halogenated substance: I, Br, Cl, H en F Odor, Taste, Yeasts, Various fermentation products, Non-polar substances

(Substances which are non soluble in water)

Description of adsorption:

Molecules from liquid phase will be attached in a physical way to a surface, in this case the surface is from the active carbon. The adsorption process takes place in three steps:

Macro transport: The movement of organic material through the macro-pore system of the active carbon (macro-pore >50nm)

Micro transport: The movement of organic material through the meso-pore and micro-pore system of the active carbon (micro-pore <2nm; meso-pore 2-50nm)

Sorption: The physical attachment of organic material on the surface of active carbon in the meso-pores and micro-pores of the active carbon

The activity level of adsorption is based on the concentration of substance in the water, the temperature and the polarity of the substance. A polar substance (substance which is good soluble in water) cannot or is badly removed by active carbon, a non-polar substance can be removed totally by active carbon.

Factors that influence the performance of active carbon in water:

The type of compound to be removed. Compounds with high molecular weight and low solubility are better absorbed.

The concentration of the compound to be removed. The higher the concentration, the higher the carbon consumption.

Presence of other organic compounds which will compete for the available adsorption sites.

The pH of the waste stream. For example, acidic compounds are better removed at lower pH.

Chemicals are classified by their probability of being efficiently adsorbed by active carbon in aqueous medium in 4 types:

1. Chemicals with very high probability of being adsorbed by active carbon: 2. Chemicals with high probability of being adsorbed by active carbon3. Chemicals with moderate probability of being adsorbed by active carbon4. Chemicals for which adsorption with active carbon is unlikely to be effective.

Toxic organic pollutant phenol is categorized in Chemicals with high probability of being adsorbed by active carbon.

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CHAPTER 2

OBJECTIVES

OF

THE STUDY

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2. OBJECTIVES AND SCOPE OF STUDY

Objectives of the study:

The aims & objectives are to study “underground water quality of Surat city” and

Potential of Rice Husk and Rice Husk Ash for Phenol Removal in Aqueous

Systems.

To check the present quality of underground water with reference to pH,

Electrical conductance (EC), Total Hardness (TH), Total alkalinity, Fluoride and

Phenols (meta- ortho- para substituted phenols).

To Determine Moisture, Volatile matter, Ash content and Fixed carbon of Rice

Husk by proximate analysis.

To Study the adsorption of phenol under varying experimental conditions of

Phenol concentration, Adsorbent dose and pH.

Scopes of the study:

To know the present quality of underground water with reference to pH, electrical conductance (EC), Total Hardness (TH), Total alkalinity, Fluoride and Phenols of surat city and GIDC area.

Is Groundwater of Surat city is contaminated by Phenols because of dyeing and printing industries effluent?

Possibility of Rice husks and Rice husk ash for removal of phenol from aqueous solution.

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CHAPTER 3

LITRATURE REVIEW

OF

THE STUDY

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3. LITRATURE REVIEW OF THE STUDY

3.1 Cases of Phenol contamination in groundwater:

Case study 1: Phenol poisoning due to contaminated Groundwater in Wisconsin.

On july 16 1974 several cars of a freight train derailed in rural southern Wisconsin (Midwestern state in north central United States) near the town of east troy. One of the cars contained 100% phenol approximately 37,900 L spilled. Recovery operations began immediately and a large amount of spilled phenol was removed by excavating soil at the spill site and transporting it to manufacturer for disposal. Caution was taken to prevent human contact with the chemical. Accidental spillage of 100% phenol (carbolic acid) in july 1974 caused chemical contamination of wells in rural area of southern Wisconsin. Groundwater samples collected by the Wisconsin department of natural resources in two nearby wells of 3.2 mg/l and 0.21 mg/l. further testing was done after a month in six wells nearest spill site, revealed peak concentrations between 15 and 126 mg/l. Human illness characterized by diarrhea, mouth sores, dark urine and burning of mouth reported by 17 individuals who consumed the contaminated water

Case study 2: Leachate Characterization and assessment of Groundwater pollution near municipal solid waste landfill site.

Suman Mor a*, Khaiwal Ravindra b, R. P. Dahiyaa and A. Chandra a aCentre for Energy Studies, Indian Institute of Technology Delhi, Hauz Khas, New Delhi-110016, India bMicro and Trace Analysis Centre, Department of Chemistry, University of Antwerp, Universiteitsplein 1, B-

2610 Antwerp, Belgium

Abstract: Leachate and groundwater samples were collected from Gazipur landfill-site and its adjacent area to study the possible impact of leachate percolation on groundwater quality. Concentration of various physico-chemical parameters including heavy metal (Cd, Cr, Cu, Fe Ni, Pb and Zn) concentration and microbiological parameters {total coliform (TC) and faecal coliform (FC)} were determined in groundwater and leachate samples. The moderately high concentrations of Cl-, NO3-, SO42-, NH4+, Phenol, Fe, Zn and COD in groundwater, likely indicate that groundwater quality is being significantly affected by leachate percolation. Further they proved to be as tracers for groundwater contamination. The effect of depth and distance of the well from the pollution source was also investigated. The presence of TC and FC in groundwater warns for the groundwater quality and thus renders the associated aquifer unreliable for domestic water supply and other uses. Although

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some remedial measures are suggested to reduce further groundwater contamination via leachate percolation, the present study demand for the proper management of waste in Delhi. A very low concentration of phenol was also observed in water samples and its concentration varied from nd to 0.1 mg l-1,

3.2 Case Studies: On Adsorption of phenol by Rice Husks and Rice Husk Ash

Case study 1: Potential of Rice Husk and Rice Husk Ash for Phenol Removal in Aqueous Systems

1A. H. Mahvi, 2A. Maleki and 3A. Eslami1Department of Environmental Health Engineering,Center for Environmental

ResearchTehran University of Medical Sciences, Tehran, Iran

2Department Environmental Health EngineeringKordestan University of Medical Sciences, Sanandaj, Iran3Department of Environmental Health, Faculty of Health

Zanjan University of Medical Sciences, Zanjan, Iran.

Abstract: The potential of rice husk and rice husk ash for phenol adsorption from

aqueous solution was studied. Batch kinetics and isotherm studies were carried out under varying experimental conditions of phenol concentration, adsorbent dose and pH. Adsorption equilibrium of rice husk and rice husk ash was reached within 6 hr for phenolic concentration 150-500 μg/L and 3 hr for phenol concentration 500-1300 μg/L, respectively. Kinetics of adsorption obeyed a first-order rate equation. The adsorption of phenol increases with increasing the solution pH value. A comparative study showed that rice husk ash is very effective than rice husk for phenol removal. The studies showed that the rice husk ash can be used as an efficient adsorbent material for removal of phenolic from water and wastewater.

Materials and Methods:

The rice husks used were obtained from the north part of Iran. The proximate and ultimate analysis of rice husks was done. The rice husk were crushed and sieved with a 30-mesh siever. Then, the husks were thoroughly washed distilled water to remove all dirt and were dried at 100ºC till constant weight. The dried husks were stored in desiccator until used. The rice husk ash obtained from burning of rice husk in electrical oven at 400 ºC for 3 hours.

The test solutions were prepared by diluting of stock solution of phenol to the desired concentrations. A stock solution was obtained by dissolving 1.0g of phenol, (obtained from Merek), in cooled distilled water and dilute to 1000 ml. Intermediate phenol

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solution was obtained by dissolving 100 ml of stock solution of phenol in distilled water and dilute to 1000 ml and finally, standard phenol solution prepared by dissolving 100 ml intermediate phenol solution in distilled water and dilute to 1000 ml. The range in concentrations of phenol prepared from standard solution varied between 100μg/L to 1000μg/L. Before mixing the adsorbent, the pH of each test solution was adjusted to the required value with diluted and concentrated H2SO4 and NaOH solution, respectively.

Absorption Studies: Sorption studies were conducted in a routine manner by the batch technique. Each phenol solution was placed in 250 ml beakers and a known amount of rice husk (1 to 7g), and rice husk ash (0.1 to 0.5g) were added to each beaker. The flasks were agitated on a shaker at a100 rpm constant shaking rate for 6hr to ensure equilibrium was reached. For the studies with the rice husk, before analysis, samples were distilled by distillation apparatus according to standard methods. Then, distilled samples analyzed for the remaining phenol. The studies were performed at a constant temperature of 25ºC to be representative of environmentally relevant condition. Kinetic experiments were conducted using a know weight of adsorbent dosage and employing phenol concentration. Finally the suitability of the Freundlich and Langmuir adsorption model to the equilibrium data were investigated for phenol - sorbent system. All the experiments were carried out in duplicates and the average value were used for further calculations.

Analysis of Phenol: The concentration of residual phenol in the sorption medium was determined with direct photometric method. At the end, after the preparation of samples according to the standard methods, the residual phenol concentrations were measured using a spectrophotometer equipment (spectrophotometer DR-2000, HACH). The absorbance of the colored complex of phenol with 4- aminoantipyrine was read at 500 nm.

Result and discussion of the study: The adsorption of phenol in aqueous solution on rice husk and its ash were examined by optimizing various physicochemical parameters such as; pH, contact time, and the amount of adsorbent and adsorbate.

Effect of Initial pH: The adsorption of phenol from aqueous solution is dependent on the pH of the solution, which affects the surface charge of the adsorbent, degree of ionization and speciation of the adsorb ate species. The adsorption of phenol by rice husk and its ash were studied at various pH values [5, 7, 8, 12, 20].The results are displayed that adsorbed amount decreases with increasing the pH value. This can be attributed to the depending of phenol ionization on the pH value.

Effects of Adsorbent Amount: The amount of adsorbent on the efficiency of adsorption was also studied.show the removal of phenol by rice husk and its ash at the solution pH of 7. Adsorbent dosage was varied from 1g to 7g and 0.1g to 0.5g for rice husk and its ash, respectively.

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The results show that for removal of 500 μg/l of phenol in 100 ml of solution, a minimum dosage of 0.3gr of rice husk ash is required for 96% removal of phenol. But, with this condition by rice husk, the removal efficiency is 27%. It is evident that for the quantitative removal of different value of phenol in 100 ml a high dosage of rice husk is required. The data clearly shows that the rice husk ash is more effective than rice husk for removal of phenol. The results also clearly indicate that the removal efficiency increases up to the optimum dosage beyond which the removal efficiency is negligible (especially about ash).

Effect of Initial Phenol Concentration: The equilibrium sorption capacities of the sorbents obtained from experimental data at different initial phenol concentration. As seen from results, the sorption capacities of the sorbents increased with increasing phenol concentration while the adsorption yields of phenol showed the opposite trend. When the initial phenol concentration was increase from 150 μg/L to 350μg/L on rice husk and from 500μg/L to 1300μg/L on rice husk ash, the loading capacity increased from 1.56×10-6 mg/mg to 1.96×10-6 mg/mg of rice husk, and from 2.7×10-4 mg/mg to 6.15×10-4 mg/mg of rice husk ash. Increasing the mass transfer driving force and therefore the rate at which phenol molecules pass from the bulk solution to the particle surface. This would results in higher phenol adsorption.On a relative basis, however, the percentage adsorption of phenol decreases as the initial phenol concentration increases. The equilibrium uptake and adsorption yield were highest for the rice husk ash, which was expected, because of the greater specific surface area and the microporous structure of rice husk ash compared with rice husk.

CONCLUSION: In this study, the ability of rice husk and rice husk ash to bind phenol was investigated as a function of pH and initial phenol concentration. Rice husk and rice husk ash adsorption capacity were strongly dependent on the pH of the solution. The sorption capacity was decreased with an increase in the pH and an increase in the initial phenol concentration. Although rice husk ash had a higher adsorption capacity (0.886 mg/g) for phenol, the experimental results indicate that rice husk's ability to adsorb phenol and, consequently, its possible utilization in the treatment of phenol-contaminated solution, its adsorptive capacity was limited. On the bases of this study, it may be concluded that rice husk and its ash especially, may be used as low-cost, natural and abundant sources for the removal of phenol. They may also be effective in removing other harmful species such as heavy metal ions present in effluents.

Case study 2: Removal of phenol from aqueous solution by Rice Husk Ash and activated carbon

M. Kermani, H. Pourmoghaddas, B. Bina And Z. Khazaei

Department of environmental health engineering, school of public health,

Isfahan university of Medical science, Isfahan, Iran.

25


Department of Biostatistics, school of public health, Isfahan University of medical science, Isfahan, Iran.

Abstract: Experiments have been conducted to examine the liquid phase adsorption of phenol from rice husk and granular activated carbon. In this experiment Rice husk ash was prepared in three different temperatures 300, 400 and 500 °C. batch kinetics and isotherm studies were carried out to evaluate the effect of contact time, pH, initial phenol concentration and adsorbent dose. Batch kinetic studies showed that the equilibrium time of 5 hr was needed for the adsorption of 10 mg/l phenol concentration maximum phenol adsorption study of Rice husk ashes prepared at 300, 400 and 500 °C and granular activated carbon was 0.925, 1, 0.989 and 1 mg phenol/gram adsorbent , respectively. Batch studies indicated that the optimum pH for the adsorption of phenol was 5 at 21 °C. the capacity of phenol adsorption at equilibrium increased with the increase of initial phenol concentration (10-300 mg/l) and decrease with the increase of adsorbent dose (1-10 gm/l) kinetic of adsorption obeyed a first order rate equation. The suitability of Freundlich and Langmuir adsorption model to the equilibrium data were investigated for each phenol-sorbent system. The result showed that the equilibrium data for Rice husk ashes prepared at 400 and 500 °C and granular activated carbon could be well by the Freundlich isotherm model, whereas the equilibrium data for Rice husk ash were prepared at 300 °C fitted the Langmuir isotherm model best within the concentration range studied. The studies showed that the Rice husk ash could be used as a new and efficient adsorbent material for the removal of phenol from the aqueous solutions.

Case study 3: Adsorption and detection of some phenolic compounds by rice huskash of Kenyan origin

Damaris N. Mbui, Paul M. Shiundu,*{ Rachel M. Ndonye and Geoffrey N. KamauDepartment of Chemistry, University of Nairobi, P.O. Box 30197, Nairobi, Kenya.

Abstract: Rice husk ash (RHA) obtained from a rice mill in Kenya has been used as an inexpensive and effective adsorbent (and reagent) for the removal (and detection) of some phenolic compounds in water. The abundantly available rice mill waste was used in dual laboratory-scale batch experiments to evaluate its potential in: (i) the removal of phenol, 1,3-dihydroxybenzene (resorcinol) and 2-chlorophenol from water; and (ii) the detection of 1,2-dihydroxybenzene (pyrocatechol) and 1,2,3-trihydroxybenzene (pyrogallol) present in an aqueous medium. The studies were conducted using synthetic water with different initial concentrations of the phenolic compounds. The effects of different operating conditions (such as contact time, concentration of the phenolic compounds, adsorbent quantity, temperature, and pH) were assessed by evaluating the phenolic compound removal efficiency as well as the extent of

26


their color formation reactions (where applicable). RHA exhibits reasonable adsorption capacity for the phenolic compounds and follows both Langmuir and Freundlich isotherm models. Adsorption capacities of 1.53 6 1024, 8.07 6 1025, and 1.63 6 1026 mol g21 were determined for phenol, resorcinol and 2-chlorophenol, respectively. Nearly 100% adsorption of the phenolic compounds was possible and this depended on the weight of RHA employed. For the detection experiments, pyrocatechol and pyrogallol present in water formed coloured complexes with RHA, with the rate of colour formation increasing with temperature, weight of RHA, concentration of the phenolic compounds and sonication. This study has proven that RHA is a useful agricultural waste product for the removal and detection of some phenolic compounds.

Case study 4: Application of agricultural fibers in pollution removal from aqueous solution

A. H. MahviSchool of Public Health, Center for Environmental Research, Medical Sciences/ University of

Tehran, Tehran, Iran

Abstract: Discharging different kinds of wastewater and polluted waters such as domestic, industrial and agricultural wastewaters into environment, especially to surface water, can cause heavy pollution of this body sources. With regard to increasing effluent discharge standards to the environment, high considerations should be made when selecting proper treatment processes. Any of chemical, biological and physical treatment processes have its own advantages and disadvantages. It should be kept in mind that economical aspects are important, too. In addition, employing environment friendly methods for treatment is emphasized much more these days. Application of some waste products that could help in this regard, in addition to reuse of these waste materials, can be an advantage. Agricultural fibers are agricultural wastes and are generated in high amounts. The majority of such materials are generated in developing countries and, since they are very cheap, they can be employed as biosorbents in water and wastewater applications. Polluted surface waters, different wastewaters and partially treated wastewater may be contaminated by heavy metals or some organic matters and these waters should be treated to reduce pollution. The results of investigations show high efficiency of agricultural fibers in heavy metal and phenol removal. In this paper, some studies conducted by the author of this article and other investigators are reviewed.

27


Indian Standard specifications for drinking water (IS: 10500)

Sr. No.

Parameter Desirable Limit

1 pH 6.5 to 8.5

2 EC (electric conductivity) 0.005 – 0.05 S/m

3 Fluoride 0.6 to 1.2 mg/l

4 Total Hardness 300 mg/l

5 Total Alkalinity 200 mg/l

6 Phenols 0.001 – 0.003 mg/l

28


CHAPTER 4

METHODOLOGY

OF

THE STUDY

29


Red circle – Industrial area, Black circle- Residential area.

30

SAMPLING LOCACTION


4. METHODOLGY:

4.1 Study Area:

The Surat city is located on the bank of river Tapi, at 21.112’ North altitude & 72.814’

east latitude.

The summers are quite hot with temperatures ranging from 37.78oC to 44.44oC. The

climate is pleasant during the monsoon while autumn is temperate. The winters are not

very cold but the temperatures in January range from 10oC to 15.5oC. The average annual

rainfall of the city has been 1143 mm.

Surat city is divided in to two zones.

RESIDENTIAL ZONE INDUSTRIAL ZONE

4.2 Sampling Locations: In these zones 10 sampling point were selected to achieve the objectives of the study. Out of them 5 are Residential zones and 5 are Industrial zones. The name of the different sampling points in the city are;

Sr. n. Location Area Source of water supply

1 Dumas chaar rasta Residential Well

2 VNSGU Residential Bore well

3 Pandesara Housing East Residential Bore well

4 Pandesara housing West Residential Bore well

5 Sachin Residential Bore well

6 Udhna GIDC(QSM) East Industrial Bore well

7 Udhna GIDC West Industrial Bore well

31


8 Pandesara GIDC East Industrial Bore well

9 Pandesara GIDC West Industrial Bore well

10 sachin GIDC Industrial Bore well

Water samples from the selected sites were collected during 17-02-10 to 24-03-10 were

collected in pre-cleaned polyethylene bottles.

The samples after collection were immediately placed in dark boxes and processed within

6 hr of collection.

Samples were collected in time during 10 am to 12 am.

Study of adsorption of phenol by rice husk and rice husk ash was done during 26-03-10

to 10-04-10

4.3 Analysis Methods:

pH:

Apparatus: Digital pH meter (HACH, Session 5 digital meter), beaker etc.

Electric conductivity:

Apparatus: Digital HACH conductivity meter, beaker etc.

FLUORIDE SPADNS Method:

Items: SPADNS reagent Solution, Deionized Water, pipette, Sample cells, tissue paper etc.

SPADNS reagent solution method:

1. Touch HACH programme select programme 190fluoride. Touch start.2. Blank Preparation:

Pipette 10.0 mL of deionized water into a dry sample cell. Carefully pipette 2.0 mL of SPADNS reagent into each cell. Swirl to mix. Start the instrument timer. A one-minute

32


reaction period will begin. When the timer expires, insert the blank into the cell holder. ZERO the instrument. The display will show: 0.00 mg/L F–

3. Prepare Sample: Pipette 10.0 mL of sample into a dry sample cell and add 2ml SPADNS reagent in to it, Swirl to mix. Give 1 minute reaction time. Insert the prepared sample into the cell holder. READ the result in mg/L F–.

TOTAL HARDNESS

Reagents:

a) Buffer solution: dissolve 16.9gm ammonium chloride (NH4Cl) in 143ml conc.

Ammonia & dilute to 250ml with distilled water. Store in plastic bottle.

b) Eriochrome black T: dissolve 0.5gm Eriochrome black T in 100gm KCl.

c) Standard EDTA solution, 0.02N: dissolve 3.723gm disodium salt ethylenediamine

tetra acetate dehydrates in distilled water & dilute to 1000ml with distilled water.

Apparatus:

Burette, pipette, conical flask, beaker, etc.

Experimental:

Take 10ml of test sample in conical flask, add buffer solution & titrate immediately with

0.02N EDTA using eriochrome black T as indicator till sky green color obtain from wine

red color. Note down the B.R. & calculate the hardness as follows.

Calculation: A x B ×1000

Hardness mg /L as CaCO3 =

mL sample taken

33


Where, A = ml titration for sample

B = mg CaCO3 equivalent to 1 ml EDTA titrant.

TOTAL ALKALINITY

Reagents:

a) standard Sulphuric acid solution,0.02N

b) methyl orange indicator solution

c) phenolphthalein indicator solution

Apparatus:

Burette, pipette, conical flask, beaker, etc.

Experimental:

Take 25ml test sample into conical flask & add distilled water. Add 2-3 drops of

phenolphthalein if pink color develops then titrate against 0.02N H2SO4 solution till

disappearance of pink color. Note down the B.R. (A). Continue the titration using methyl

orange indicator till color changes from yellow to orange. Note the B.R. (B) & calculate

the alkalinity of the solution as follows.

Calculation:

34


Phenolphthalein alkalinity as mg/L = B.R (B) ×N×50,000/ml of sample taken

Mehtyl Orange Alkalinity as mg /L = B.R (B) ×N×50,000/ml of sample taken.

PHENOLICS (4-AAP method With Distillation)Reagents:

Phosphoric acid solution, 1 + 9: Dilute 10 mL of 85% H3PO4 to 100 mL with distilled water.

Copper sulfate solution: Dissolve 100 g CuSO4C5H2O in distilled water and dilute to 1 liter.

Buffer solution: Dissolve 16.9 g NH4Cl in 143 mL conc. NH4 OH and dilute to 250 mL with distilled water. Two mL should adjust 100 mL of distillate to pH 10.

Aminoantipyrine solution: Dissolve 2 g of 4AAP in distilled water and dilute to 100 mL.

Potassium ferricyanide solution: Dissolve 8 g of K3Fe(CN)6 in distilled water and dilute to 100 mL.

Stock phenol solution: Dissolve 1.0 g phenol in freshly boiled and cooled distilled water and dilute to 1 liter. 1 mL = 1 mg phenol.

Working solution A: Dilute 10 mL stock phenol solution to 1 liter with distilled water. mL = 10 Fg phenol.

Working solution B: Dilute 100 mL of working solution A to 1000 mL with distilled water. 1 mL = 1 Fg phenol.

Ferrous ammonium sulfate: Dissolve 1.1 g ferrous ammonium sulfate in 500 mL distilled water containing 1 mL conc. H2SO4 and dilute to 1 liter with freshly boiled and cooled distilled water.

Procedure:

Distillation:

Measure 500 mL sample into a beaker. Lower the pH to approximately 4 with H3PO4 , add 5 mL CuSO4 solution and transfer to the distillation apparatus. Distill 450 mL of sample, stop the distillation, and when boiling ceases add 50 mL of warm distilled water to the flask and resume distillation until 500 mL have been collected.

Direct photometric method

Using working solution A prepare the following standards in 100 mL volumetric flasks.mL of working solution A Conc. Fg/L

35


• To 100 mL of distillate or an aliquot diluted to 100 mL and/or standards, add 2 mL of buffer solution (7.3) and mix. The pH of the sample and standards should be 10 ± 0.2.

• Add 2.0 mL aminoantipyrine solution and mix. Add 2.0 mL potassium ferricyanide solution and mix.

• After 15 minutes read absorbance at 510 nm.

CalculationPrepare a standard curve by plotting the absorbance value of standards versus the corresponding phenol concentrations. Obtain concentration value of sample directly from standard curve.

Proximate Analysis of Rice Husk:

Material: Rice Husks

Apparatus: Analytical balance, Electrical oven, Dessicator, Muffle furnace, Crucible, pair of tongs

Procedure:

(1) Determination of inherent moisture:

The rice husks are washed thoroughly with distilled water 2 to 3 times then dry at 105°C. The sample then dried in air, weight crucible in analytical balance accurately. Transfer one gram of air dried sample in the crucible and weight. The crucible is kept inside the electrical oven maintained at 105 °C-110 °C temperature for an hour. After heating for an hour, crucible is kept in dessicator for cooling. On cooling it is again weighted on the analytical balance. The difference in weight is reported in percentage as the amount of inherent moisture in the sample.

(2) Volatile Matter: the dried sample after determining moisture content is heated in a muffle furnace is maintained at 950 ± 25 °C for exactly 7 minutes. The sample is taken in a crucible and heated with lid. After heating the crucible is removed from muffle furnace with the help of long leg tong carefully. It is first put on a cool iron plate and then transfer the warm crucible in dessicator. Once it attained the room temperature it is finally weighted. Loss in weight is reported as volatile matter on percentage basis.

(3) Ash Content: the residue in the crucible is then heated inside muffle furnace at 725 ± 25 °C for half an hour, heating of crucible is done without covering lid. The crucible is then cooled first in air and then in dessicator. The amount of unburnt residue in crucible is ash which can be reported in percentage.

36


(4) Fixed carbon: the sum total of percentage of volatile matter, moisture and ash subtracted from 100 gives the estimate amount of fixed carbon.

Calculations:

(1) Moisture:

Heat the sample at 105 – 110 °C for one hour in electric oven.

Weight of the empty crucible = X1 gm

Weight of crucible + sample = X2 gm

Weight of sample = X2 - X1 gm

Weight of crucible + sample after heating = X3 gm

Weight of sample after heating = X2 - X3 gm

% of moisture A =

(2) Volatile matter:

Heat the sample after moisture in muffle furnace at 950 °C for 7 minutes.

Weight of crucible + sample after heating = X4 gm

% of volatile matter + moisture B =

37

X2 – X4

×100

X2 - X1

X2 – X4

×100

X2 - X1

X2 - X3

×100

X2 - X1

X2 - X3

×100

X2 - X1

-

X4 – X5

×100

X2 - X1


% of volatile Matter C =

(3) Ash:

Heat the sample after step two in muffle furnace at 725 °C for 30 minutes.

Weight of crucible + ash = X5 gm

% of Ash D =

(4) Fixed carbon:

% of Fixed carbon = 100 – (% of Moisture (A) + % volatile Matter (B) + % of Ash (D))

Process of Phenol removal by Rice husk and Rice husk ash:

Preparation of sorbent: Rice husk used were obtained from south part of Gujarat in India. The species name is JAYA Rice. Rice Husks were thoroughly washed by distilled water to remove all dirt and were dried at 105 °C. The dried husks were stored in desiccators until used. The Rice husk ash obtained from burning of Rice husk in muffle furnace at 400 °C for 3 hours. Rice husk ash was stored in desiccators until used.

Chemicals:

The test solutions were prepared by diluting of stock solution of phenol to the desired concentrations. A stock solution was obtained by dissolving 1.0g of phenol, in distilled water and dilute to 1000 ml. Intermediate phenol solution was obtained by dissolving 100 ml of stock solution of phenol in distilled water and dilute to 1000 ml and finally, standard phenol solution prepared by dissolving 100 ml intermediate phenol solution in

38


distilled water and dilute to 1000 ml. pH of each test solution was adjusted to the required value with diluted and concentrated H2SO4 and NaOH solution, respectively. All pH measurement were carried out with a digital HACH pH meter.

Absorption Studies:

Adsorption study of phenol by Rice husks and Rice husk ash were carried out under varying experimental conditions of pH, Phenol concentration and Adsorbent dose.

(1) pH:

Each phenol solution was placed in 250 ml conical flask. Total eight standard phenol solution of 1 mg/100ml were prepared. Out of them four standard solutions were used for Rice husk ash and remaining four were used for Rice husk. Various pH prepared for adsorption study were respectively 5, 7, 9, 11 from acidic to alkalic for both Rice husk and Rice husk ash. Rice husk ash added to each four conical flask was in amount of 0.4 gm. Rice husk were added in amount of 3 gm in remaining four flasks. Then all the eight conical flasks of both Rice husk and Rice husk ash were putted on shaker at 150rpm constant shaking rate for 3 hour. Solutions with Rice husk ash were analyzed without distillation while Rice husk samples were distilled by distillation apparatus according to standard methods. Then distilled samples were analyzed for remaining phenol by standard method described in APHA.

(2) Phenol Concentration:

In this study various concentrations of standard phenol solutions were prepared. Prepared solutions were respectively 0.2, 0.4, 0.6 and 0.8 mg/100ml for both Rice husk and Rice husk ash. Amount of rice husk taken for adsorption was 0.4 gm and amount of Rice husk ash and Rice husk used were accordingly 0.4 gm and 3 gm. pH of the solutions were made neutral. After all this all the eight flasks were putted on shaker at 150rpm for three hours for reaction. Solutions with Rice husk ash were analyzed without distillation while Rice husk samples were distilled by distillation apparatus according to standard methods. Then distilled samples were analyzed for remaining phenol by standard method described in APHA.

(3) Adsorbent dose:

Experiment carried out with the study of effect of different weight of Rice husk ash and Rice husk on the removal of phenol. Various weight of Rice husk ash 0.1 gm, 0.2gm. 0.3gm and 0.4gm were used for the adsorption study. Rice husk of different weight 1gm, 2 gm, 3 gm, 4 gm used. pH for all eight solutions were made neutral, concentration of phenol solution 1mg/100ml made for all eight samples. Then all the eight conical flasks of both Rice husk and Rice husk ash were putted on shaker at 150rpm constant shaking rate for 3 hour. Solutions with Rice husk ash were analyzed without distillation while Rice husk samples were distilled by distillation apparatus according to standard methods. Then

39


distilled samples were analyzed for remaining phenol by standard method described in APHA.

CHAPTER - 5

RESULT

AND

DISCUSSION40


5. RESULT AND DISCUSSION

5.1 Groundwater Analysis5.1(a) Groundwater Quality of Surat city on 22nd February 2010

Location pH EC S/m F- mg/l Total Hardness

mg/l

Total Alkalinity

mg/l

phenols mg/l

Dumas Chaar Rasta 7.6 0.119 0.42 431 326 BDL

VNSGU 7.6 0.942 0.75 2122 291 BDL

Pandesara Housing East

8.0 0.761 0.50 2157 333 BDL

Pandesara Housing West

7.9 0.545 0.48 1732 475 BDL

Sachin 7.4 0.160 0.79 478 450 BDL

Udhna GIDC (QSM) East

7.7 0.578 0.56 1552 381 BDL

Udhna GIDC West 8.0 0.321 0.51 939 538 0.005

Pandesara GIDC East 7.8 0.062 0.58 199 210 0.063

Pandesara GIDC West 7.9 1.461 0.82 4015 368 BDL

Sachin GIDC 7.8 0.261 1.49 151 656 0.006

41


5.1 (b) Groundwater Quality of Surat city on 15th March 2010

42

Location pH EC S/m F- mg/l Total Hardness

mg/l

Total Alkalinity

mg/l

phenols mg/l


VNSGU 7.6 0.950 0.89 2110 297 BDL


7.6 0.779 0.42 2143 331 BDL


7.5 0.515 0.50 1746 469 BDL

Sachin 7.4 0.150 0.69 482 454 BDL


7.7 0.590 0.58 1548 379 BDL

Udhna GIDC West 8.2 0.355 0.47 941 542 0.007

Pandesara GIDC East

8.0 0.0607 0.52 201 214 0.081

Pandesara GIDC West

7.7 1.361 0.80 4005 360 BDL

Sachin GIDC 7.8 0.287 1.55 149 664 0.006


5.1(c) Groundwater Quality Average Value:

Location pH EC S/m F- mg/l Total Hardness mg/l

Total Alkalinity mg/l

Phenols mg/l


VNSGU 7.6 0.946 0.82 2116 295 BDL


7.8 0.774 0.46 2150 332 BDL


7.7 0.53 0.49 1739 472 BDL

Sachin 7.4 0.155 0.74 480 452 BDL


7.7 0.584 0.57 1550 380 BDL

Udhna GIDC West 8.1 0.338 0.49 940 540 0.005

Pandesara GIDC East

7.9 0.0616 0.55 200 212 0.072

Pandesara GIDC West

7.8 1.414 0.81 4010 364 BDL

Sachin GIDC 7.8 0.274 1.52 150 660 0.006

43


5.1 (d) Charts from Table 5.1 (c) value

44


45


46


5.2 Proximate Analysis of Rice Husk:

Proximate analysis of rice husk carried to find out Moisture, volatile matter, Ash content and Fixed carbon present in original weight of Rice husk. This is further useful in adsorption study of Rice husk ash.

47


5.3: Adsorption study of Rice husk and Rice husk ash

5.3 (A) Effect of pH on the Removal of Phenol by Rice Husk and Rice Husk Ash (Rice Husk Dosage = 3 gm, Rice Husk Ash Dosage = 0.4 gm Phenol Concentration = 1 mg/100ml at 150 rpm for 3 hour )

The results are displayed in Figure Shows that adsorbed amount of phenol decreases with increasing the pH value. This can be attributed to the depending of phenol ionization

48

pH of Phenol solution (1mg/100ml)

Removal efficiency of Rice Husk (3gm) in %

5 62.3 %

7 52.9 %

9 22 %

11 9 %

pH of Phenol solution (1mg/100ml)

Removal efficiency Rice Husk Ash (0.4gm) in %

5 98.2 %

7 92.4 %

9 86.9 %

11 53 %


on the pH value. Phenol, which is a weak acid (pKa=10), will be adsorbed to a lesser extent at higher pH values due to the repulsive force prevailing at higher pH value. It also forms salts in the higher pH range, which readily ionize leaving negative charge on the phenolic group. At the same time the presence of OH(negative) ions on the adsorbent prevents the uptake of phenolate ions. pH also affects the surface properties of the sorbent, At very low pH values, the surface of the sorbent would also be surrounded by the Hydronium ions, which enhance the phenol interaction with binding site of the sorbent by greater attractive forces, hence its uptake on polar adsorbent is reduced

5.3(B) Effect of Rice Husk and Rice husk ash on the Removal of Phenol for Various Phenol Concentrations: (Rice Husk Dosage = 3 gm, Rice Husk Ash Dosage = 0.4 g, at pH 7.5 and at 150 rpm for 3 hour)

Phenol Concentration

Removal efficiency

of Rice Husk Ash (0.4 gm)

in %

0.2 mg/100ml 98.9 %

0.4 mg/100ml 96.3 %

0.6 mg/100ml 97 %

0.8 mg/100ml 94.4 %

Line chart of Effect of Rice Husk and Rice husk ash on the Removal of Phenol for Various Phenol Concentrations:

49

Phenol Concentration

Removal efficiency of Rice Husk (3gm) in %

0.2 mg/100ml 81.3 %

0.4 mg/100ml 76 %

0.6 mg/100ml 74 %

0.8 mg/100ml 51.7 %


The adsorption was highest for the rice husk ash, which was expected, because of the greater specific surface area and the microporous structure of rice husk ash compared with rice husk. It also shows that higher amount of Rice husk is needed when concentration of phenol increase.

5.3 (C) Effect of Weight of Rice Husk and Rice Husk ash on the Removal of Phenol (phenol concentration 1 mg/100ml, pH 7.5 at 150 rpm for 3 hr)

50

Rice Husk weight in

Gram

Phenol Removal efficiency

in %

1 gm 12.4 %

2 gm 20 %

3 gm 58.7 %

4 gm 62.7 %

Rice Husk Ash

weight in Gram

Phenol Removal

efficiency in %

0.1 gm 63 %

0.2 gm 83.9 %

0.3 gm 92.3 %

0.4 gm 96 %

mg/100ml


The amount of adsorbent on the efficiency of adsorption was also studied. Figures show the removal of phenol by Rice husk and its ash at the solution pH of 7. Adsorbent dosage was varied from 1g to 4g and 0.1g to 0.4g for rice husk and its ash, respectively. The results show that for removal of 1 mg/l of phenol in 100 ml of solution, a minimum dosage of 0.4gr of rice husk ash is required for 96% removal of phenol. But, with this condition by rice husk, the removal efficiency is very less. It is clear that for the quantitative removal of different value of phenol in 100 ml a high dosage of Rice husk is required. The data clearly shows that the Rice husk ash is more effective than Rice husk for removal of phenol. The results also clearly indicate that the removal efficiency increases up to the optimum dosage.

51

Line chart of Effect of Weight of Rice Husk ash on the Removal of Phenol

Line chart of Effect of Weight of Rice Husk on the Removal of Phenol


CONCLUSIONS

• All the places have EC value greater than 0.05 Siemens/meter, so the Groundwater cannot be use for drinking purpose.

• Except Pandesara GIDC East and Sachin GIDC all the places have Total Hardness value high.

• All the places have Total Alkalinity value high

• Only one place Sachin GIDC have Fluoride value higher than IS: 10500 limit.

• Phenols are found in Pandesara GIDC East, Udhna GIDC West and Sachin GIDC higher than IS: 10500 maximum limit.

• It is recommended that effluents from industries must be properly treated before discharge in industrial areas.

• The adsorption of phenol by Rice Husk and its ash were studied at various pH values. The results show the adsorbed amount decreases with increasing the pH value.

52


• It is clear that for the quantitative removal of different value of phenol in 100 ml a high dosage of Rice Husk is required.

• The results also clearly indicate that the removal efficiency increases up to the optimum dosage of Rice Husk and Rice Husk Ash.

• The data clearly shows that the rice husk ash is more effective than rice husk for removal of phenol.

• Rice husk and its ash may be used as low-cost, natural sources for the removal of phenol. They may also be effective in removing other harmful species such as heavy metal ionspresent in effluents.

53


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13) Greenwood, Norman N.; Earnshaw, A. (1997). Chemistry of the Elements, 2nd

Edition.

14) Black, A. P.; Babers, F. H. (1939). "Methyl nitrate". Org. Synth.; Coll. Vol. 2

15) Greenwood, Norman N.; Earnshaw, A. (1997). Chemistry of the Elements, 2nd

Edition, Oxford: Butterworth-Heinemann. p. 804.

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16) Khriachtchev, Leonid; Mika Pettersson, Nino Runeberg, Jan Lundell & Markku Räsänen

17) Maton, Anthea; Jean Hopkins, Charles William McLaughlin, Susan Johnson,

Maryanna Quon Warner, David LaHart, Jill D. Wright “Human Biology and

Health”. Englewood Cliffs, (1993).

18) Vaclacik and Christian, 2003.

19) Research paper by Carole, Elizabeth, Katie, Monica, Samantha.

20) Underground Water based on Donald Bruehl's website

http://www.geocities.com/RainForest/4619/index.html

21) “Infiltration Well: A Potential Technology Option in Rural Water Supply”.

22) GEO.101-02 Introduction to Geology.

23) Frances Gies and Joseph Gie et al.

24) Literature review: part 1 – An overview of ground water quality issues.

25) P. N. Palanisamy, A. Geetha, M. Sujatha, P. Sivakumar and K.

Karunakaran,“Assessment of Ground Water Quality in and around

Gobichettipalayam Town Erode District”,

26) Nigeria Priscilla Alexander ‘Evaluation of ground water quality of Mubi town in

Adamawa State’.

27) Mayur C. Shah, Prateek G. Shilpkar and Pradip B. Acharya,“Ground Water

Quality of Gandhinagar Taluka, Gujarat, India“.

28) http://earthsci.org/education/teacher/basicgeol/groundwa/groundwa.html.29) Groundwater Contamination: Contamination, sources & hydrology By Chester

David Rail.

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