CHAPTER: 1

INTRODUCTION

1.1 BACKGROUND

Fluoride is widely dispersed in nature and is estimated to be the most

abundant element on our planet. Fluoride ion in drinking water for both

beneficial and detrimental effects on health. The world known organization and

Indian Council of Medical Research described he drinking water quality

guideline value for fluoride is 1.5 mg/l abnormal level of fluoride in water is

common in fractured hard rock zone veins. Fluoride ions from these minerals

leach into the water and contribute to high fluoride concentrations; the ground

of fluorosis in mainly due to the intake of large quantities of fluoride through

drinking water is reported in many states of India. The availability of soluble

fluoride ingested with water was nearly 100%, because soluble fluoride in

drinking water was easily absorbed by the gastrointestinal tract without

intervention of interfering elements such as Ca. Mg and Al. So, water fluoride

level is a primary factor for the cause of fluorosis. Fluorosis is a slow,

progressive, crippling malady, which affects every organ, tissue and cell in the

body and results in health complaints having overlapping manifestations with

several other diseases.The primary adverse effects associated with chronic,

excess fluoride intake are dental and skeletal Fluorosis. It also adversely affects

the cerebral function and neurotransmitters reduced intelligence in children is

associated with exposure to high fluoride levels in food and drinking water.

1
The global prevalence o fluorosis is reported to be about 32% In India, around

20 people were severely affected by fluorosis and around 40 million. Are

exposed to its risk. The number of people gets affected, the number of vinages

blocks, districts and states endemic for fluorosis ha been steadily increasing

ever since the disease was discovered in India during The reason for the

increase in the disease incidence and the lows. le number of locations being

identified as endemie zones for ihRrosis is due to overgrowth of population,

necessitating more and more water, indiscriminate digging of tube wells,

resorting to the use of hand unawareness regarding the importance of checking

water pump water, quality, especially for nuoride and due to water shortage.

Agencies responsible for water supply resort to pumping water from open

wells and tube wells to overhead tanks and supply ground water to residents.

and invariably such sources are not tested for nuoride. Based on the

entensively documented relationship between caries experience and both ater

fluoride concentration and fluoride intake, the adequate intake and

recommended dietary allowance for fluoride from all sources is set at 0.05 mg

day. This intake range is recommended for all ages greater than 6 kg months,

because it confers a high level of protection against dental caries and is

associated with no known unwanted health effects. Agencies also set the

adequate intake level for infants below 6 months at 0.01 mg day Fluorosis is a

cosmetic condition that affects the teeth and skeletal ll's caused by

overexposure to fluoride during the first eight years of life This is the time

2
when most permanent teeth are being formed After the teeth come in, the teeth

of those affected by fluorosis may appear mildly discolored. For instance, there

may be lacy white markings at only dentists can detect In more severe cases,

however, the teeth may have Stains ranging from yellow to dark brown

1. Surface irregularities

2. Pits that is highly noticeable

1.2 Wide spread of Fluorosis

• Fluorosis first attracted attention in the early 20th century Researchers

were surprised by the high prevalence of what was called "Colorado

Brown Stain" on the teeth of native-born residents of Colorado Springs.

The stains were caused by high levels of fluoride in the local water

supply. People with these stains also had an unusually high resistance to

dental cavities. This sparked a movement to introduce nuoride into

public water supplies at a level that could prevent cavities but without

causing fluorosis.

• Fluorosis affects nearly one in every four Americans ages 6 to 49. It's

most prevalent in those ages 12 to 15. The vast majority of cases are

mild, and only about 2% are considered moderate," Less than 1% are

"severe." But researchers have also observed that since the mid-1980s,

the prevalence of fluorosis in children ages 12 to 15 has increased.

3
 • Although fluorosis is not a disease. its effects can be psychologically

distressing and difficult to treat. Parental vigilance can play an important

role in preventing fluorosis.

1.3 Fluorosis Causes

• A major cause of iluorosis the inappropriate use of nu containing dental

products such as toothpaste and moiab rinses Sometimes, children enjoy

the taste of nuoridated toothpaste much that they swallow it instead of

spiting it out.

• But other things can cause fluorosis. For example, taking a hidacr than

prescribed amount of a nuoride supplement during early childhood can

cause it. So can taking a fluoride supplement when fluoridated drinking

water or nuoride-fortified fruit juices and soft drink already provide the

right amount.

1.4 Fluoride Levels in Drinking Water

• Fluoride occurs naturally in water. Natural fluoride levels above the

currently recommended range for drinking water may increase the risk

for severe fluorosis. In communities where natural levels exceed 2 parts

per million, the CDC recommends that parents give children water from

other sources.

• Prompted by concerns that children may be getting too much fluoride,

the Health and Human Services Department in January 2011 lowered its

4
 recommended level of fluoride in drinking water. And the

Environmental Protection Agency is reviewing its rules on the upper

limit of fluoride levels in drinking water.

1.5 Fluorosis Symptoms

• Symptoms of fluorosis range from tiny white specks or streaks that may be

unnoticeable to dark brown stains and rough pined enamel that s difficult to

clean. Teeth that are unaffected by fluorosis are smooth and glossy. They

should also be a pale creamy white. Contact your dentist if you notice that

your child's teeth have white Contact your streaks or spots or if you

observe one or more discolored teeth.

Since the 1930s, dentists have rated the severity of fluorosis using the

following categories:

• Questionable. The enamel shows slight changes ranging from a few

white flecks occasional white spots.

• Very mild. Small opaque paper-white areas are scattered over les then

25% of the tooth surface Mad.

• Mild. White opaque areas on the surface are more extensive but still

affect less than 50% of the surface.

• Moderate. Whole opaque areas affect more than 50% of the enamel

surface.

5
 • Severe. All enamel surfaces are affected the teeth also have pitting

that may be discrete or may ran together.

1.6 Fluorosis Treatments

• In many cases, fluorosis is so mild that no treatment is needed or,

may only affect the back teeth where it can't be seen.

• The appearance of teeth affected by moderate-to-severe fluorosis

can be significantly improved by a variety of techniques. Most of

them aimed masking the stains.

Such techniques may include:

• Tooth whitening and other procedures to remove surface stains

• Bonding, which coats the tooth with a hard resin that bonds to the

enamel

• Crowns

• Veneers, which are custom-made shells that cover the front of the

teeth to Veneers, which are improve their appearance

1.7 Fluorosis Prevention

Parental vigilance is the key to preventing fluorosis.

If your water comes from a public system, your doctor or dentist If as

well as your local water authority or public health department can tell you

how much fluoride is in it. If you rely on well water or bottled water, your

6
public health department or a local laboratory can analyze its fluoride

content. Once you know how much fluoride your child is getting from

drinking water and other sources such as fruit juices and soft drinks. you

can work with your dentist to decide whether or not your child should have

a fluoride supplement.

At home, keep all fluoride-containing products such as toothpaste. mouth

rinses, and supplements o of the reach of young children. lf a child ingests a

large amount of fluoride in a short period of time. it may cause symptoms

such as:

• Nausea

• Diarrhea

• Vomiting

• Abdominal pain

• Although fluoride toxicity usually doesn't have consequences, it sends

several hundred children to emergency rooms each year.

• It's also important to monitor your child s use of fluoridated toothpaste.

Only place a pea sized amount of toothpaste on your child's toothbrush.

That is sufficient for fluoride protection. Also teach your child to spit out

the toothpaste after brushing instead of swallowing it. To encourage

spitting. avoid toothpastes containing flavors that children may be likely

to swallow.

7
1.8 Skeletal Fluorosis

Skeletal fluorosis is a bone disease caused by excessive accumulation

of fluoride in the bones. In advanced cases, skeletal fluorosis causes pain

and damage to bones and joints.

Causes

Common causes of fluorosis include inhalation of fluoride lists fumes by

workers in industry, use of coal as an indoor fuel source common practice

in China), consumption of fluoride from drinking (naturally occurring

levels of fluoride in excess of the CDC recommended safe levels), and

consumption of fluoride from drinking particularly brick tea. Skeletal

fluorosis can be caused (Na AlF6 sodium hexafluoroaluminate), and the

disease was recognized among workers processing cryolite.

In India, the most common cause of fluorosis is fluoride- laden drinking

water which is sourced as ground water from deep bore-wells. Over half of

ground water sources in India have fluoride above recommended levels

Fluorosis can also occur as a result of the volcanic activity. The 1783

eruption of the Laki volcano in Iceland is estimated to have killed about of the

Icelandic population, and 60% of livestock, as a result of and sulfur d gases.

The 1693 eruption of Hekla also led fatalities of livestock under similar

conditions.

8
Mechanism of action

The best way to view the mechanism of action by which fluorine breaks down

bones and causes skeletal fluorosis in a stepwise fashion.

Fluorine enters the body by two paths ingestion or respiration Both paths

lead to corrosion of exposed tissue in high concentrations. Since the mort

likely form of fluorine to enter the body is hydrogen fluoride (HF) gas, this is

what starts the process Exposed tissues will be utilized by HF in neutralization

reactions.

1. This will leave F- free to pass further into the body.

2. It reacts with the concentration HCI in the stomach to form the weak

acid, HF.

3. This compound is then absorbed by the gastro-intestinal tract and passes

into the liver via the portal vein since elemental F is one of strongest oxidizers

currently known. the anion F- is immune to phase 1 metabolic reactions. which

are generally oxidation reactions, in the liver. These reactions are the Body’s

first line of defense tobio transform harmful compounds something more

hydrophilic and more easily excreted.

4. The HF is now free to pass into blood stream and be distributed to all

tissues including bones.

5. Bones are largely composed of Ca compounds. Particularly carbonated

hydroxyapatite (Ca 5(PO 4) 3(OH)); the reaction of Ca2+ ions and HF

9
6. This salt must be cleared by the body, which concomitantly leaches out

some of the calcium that would be part of the bone matrix.

This process results in increased density but decreased strength in bones.

Epidemiology

1. In some areas, skeletal fluorosis is endemic. While fluorosis is most

severe and widespread in the two largest countries -India and China UNICEF

estimates that fluorosis is endemic in at least 25 countries across the globe.

The total number of people affected is not known, but a conservative estimate

would number in the tens of millions." In India, 20 states have been identified

as endemic areas, with an estimated 60 million people at risk and 6 million

people disabled about 600.000 might develop a neurological disorder as a

consequence

Table 1.1 classification and description of bone

Osteoclerot Ash Concentration Symptoms and signs
Ic phase (mgF/kg)
Normal 500 to 1,000 Normal
Bone
Preclinical 3,500 to 5,500 Asymptomatic; slight radio
phase graphically-Detectable increases in
bone mass
Clinical 6,000 to 7,000 Sporadic pain; stiffness of joints;
Phase 1 Obsteoclerosis of pelvis and
vertebral spine
Clinical 7,500 to 9,000 Chronic joint
Phase 2 pain;arthriticsymptoms;slight
calcification of ligaments increased
osteoclarasis
and cancellouse bones; with /
without osteoporosis of long bones
Phase 3 Limitation of joint movement ;

10
 Crippling 8,400 calcification Of ligments of neck
fluorosis vertebral column; crippling
deformities of the spine and major
joints; muscle Wasting;
neurological defects / compression
of Spinal chord
Symptoms and side effects

Fig 1.1 Moroccan cow with fluorosis

Symptoms are mainly promoted in the bone structure. Due to a high

fluorine concentration in the body.the bone is hardened and thus less elastic,

resulting in an increased frequency of fractures. Other symptoms include

thickening of the bone structure and accumulation of bone tissue, which both

contribute to impaired joint mobility. Ligaments and cartilage can become

ossified. Most patients suffering from skeletal fluorosis show side effects from

the high fluorine dose such as ruptures of the stomach lining and nausea.

Fluorine can also damage the parathyroid glands. leading to

hyperparathyroidism, the uncontrolled secretion of parathyroid hormones.

These hormones regulate calcium concentration in the body An elevated

parathyroid hormone concentration results in a depletion of calcium in bone

11
structures and thus a higher calcium concentration in the blood. As a result,

bone flexibility decreases making the bone more amenable to fractures.

Effectsonanimals

The histological changes which are induced through fluorine on rats

resemble those of humans.

Treatment

As of now, there are no established treatments for skeletal fluorosis patients.

However, it is reversible in some cases, depending on the progression of the

disease. If fluorine intake is stopped, the fluorine existing in bone structures

will deplete and be excreted via urine. However, it is a very slow process to

eliminate the fluorine from the body completely. Minimal results are seen in

patients. A treatment of side effect is also very difficult. For example, a patient

with a bone fracture cannot be treated according to standard procedures,

because the bone is very brittle. In this case, recovery will take a very long

time and a pristine healing cannot be guaranteed.

1.9 DENTAL FLUOROSIS

Dental fluorosis.also called mottling of tooth enamel, is a developmental

disturbance of dental enamel caused by the consumption of excess fluoride

during tooth development. The risk of fluoride overexposure occurs at any age

but it is higher at younger ages. In its mild forms (which are its most common).

fluorosis often appears as unnoticeable, tiny white streaks or specks in the

enamel of the tooth. In its most severe form.tooth appearance is marred by

12
discoloration or brown markings. The enamel may be pitted, rough and hard to

clean. The spots and stains left by fluorosis are permanent and may darken

overtime.

Physiology

Teeth are generally composed of hydroxyapatite and carbonated

hydroxyapatite: as the intake of fluoride increases, so does the tooth

composition of fluorapatite. Excessive fluoride can cause white spots and, in

severe cases, brown stains, pitting. or mottling of the enamel. A tooth is no

longer at risk of fluorosis after eruption into the oral cavity. At this point,

fluorapatite is beneficial because it is more resistant to dissolution by acids

(demineralization). Although fluorosis usually affects permanent teeth,

occasionally the primary teeth may be involved

Risk factors for dental fluorosis

The most superficial concern in dental fluorosis is aesthetic changes in the

permanent dentition (the adult teeth). These changes are prone to occur in

children who are excessively exposed to fluoride between 20 and 30 months of

age. The critical period of exposure is between 1 and 4 years old, and the child

is no longer at risk after 8 years of age. The severity of dental fluorosis

depends on the amount of fluoride exposure, the age of the child. individual

response. and weight, degree of physical activity, nutrition, and bone growth.

Many well-known sources of fluoride may contribute to overexposure

including dentifrice/fluoridated mouth rinse (which young children may

13
swallow). Bottled waters which are not tested for their fluoride content,

inappropriate use of fluoride supplements, and ingestion of foods especially

imported from other countries, and public water fluoridation. The last of these

sources is directly or indirectly responsible for 40% of all fluorosis, but the

resulting effect due to water fluoridation is largely and typically a cases can be

caused by exposure to water that is naturally fluoridated to levels well above

the recommended levels, or by exposure to other fluoride sources such as brick

tea or pollution from high fluoride coal.

Diagnosis

The differential diagnosis for this condition may include Turner's

hypoplasia (although this is usually more localized). Some mild forms of

amelogenesis imperfect, and other environmental enamel defects of diffuse and

demarcated opacities.

Table 1.2 classification and of enamel description

Classification Criteria- description of enamel

Normal Smooth, glossy,pale creamy-white

Translucent surface.
Questionable A few white flecks or white spots
Very Small opaque,paper white areas covering less
Mild than 25%of the tooth surface
Mild Opaque white areas covering less than 50% of the
tooth surface
Moderate All tooth surface affected ; marked wear on
bitting surfaces; brown stain may be presented
Severe All tooth surface affected ;discrete or confluent
pitting; brown stain present

14
Table 1.3 dietary reference intakes for fluoride

Dietary reference intake for fluoride

AGE GROUP Reference Adequate intake Tolerable upper
weight kg ( lb ) (mg/day) intake (mg/day)

Infants 0-6 months 7(16) 0.01 0.7

Infants 7-12 months 9(20) 0.5 0.9

Children 1-3 years 13(29) 0.7 1.3

Children 4-8 years 22(48) 1.0 2.2

Children 9-13 years 40(88) 2.0 10

Boys 14-18 years 64 (142) 3.0 10

Girls 14-18 years 57(125) 3.0 10

Males 19 years and 76(166) 4.0 10

over
Females 19 years 61 (133) 3.0 10
and over
1.10 OBJECTIVE

• To obtain the fluoride endemic areas villages in Madurai.

• To collect the drinking water sources from the selected areas.

• To analyze the water samples by envirocare private limited and TWAD

board by fluoride by method.

• To compare the results obtained from TWAD board and envirocare

private limited by alizarin method previous year.

15
 CHAPTER: 2

REVIEW OF LITERATURE

Effective Low Cost Adsorbents for Removal of Fluoride from Water

KoteswaraRao M1, Mallikarjun Metre 2

Drinking water contamination by fluoride is recognized as a major public

health problem in many parts of the world. In fact, although fluoride is an

essential trace element for animals and humans, excessive fluoride intake may

cause adverse health effects. The present survey highlights on efficiency of

different materials for the removal of fluoride from water. The most important

results of extensive studies on various key factors (pH, agitation time, initial

fluoride concentration, temperature, particle size, surface area, presence and

nature of counter ions and solvent dose) fluctuate fluoride removal capacity of

materials are reviewed.

This paper investigates the potential health risks involved with both lower and

higher concentrations of fluoride in drinking water, as well as posing possible

measures of mitigation to eliminate such harmful threats. Also, this paper

describes brief discussions on various low cost adsorbents used for the

effective removal of fluoride from water. The removal capacity increases by

increasing dose of the adsorbent and decreasing size of the adsorbent. The new

treated adsorbents are also available and hope that it will encourage even more

rapid and extensive developments for the treatment of fluoride.

16
Investigation on Sorption of Fluoride in Water Using Rice Husk as an

Adsorbent WaheedS. Deshmukh, S. J. Attar and M. D. Waghmare*

The batch adsorption studies were undertaken to assess the suitability of

inexpensive adsorbent prepared from agricultural waste, rice husk. The

adsorbent was preparedby chemical impregnation method followed by physical

activation.

Static studies have aimed for investigation of fluoride removal efficiency

under the varying conditions ofthemajor parameters of adsorption, viz. pH,

dose of adsorbent, rate of stirring, contact time and initial adsorbate

concentration, and optimized by batch procedure in the mixtureof known

concentration of fluoride solution.

The optimum sorbent dose was found tobe 10g/L by varying the dose of

adsorbent from0 to 16g/L; equilibrium was achieved in120 min for the

optimum pH. It has been observed that the optimum adsorption takes place at

lower pH by varying pH from 2, 4, 6, 8, 10. Maximum fluoride removal was

observed to be 75% at optimum conditions. Freundlich as well as Langmuir

isotherms were plotted and constants of isotherms were determined.

Based on these studies, it is concluded that the biosorbent prepared from

rice husk has shown promising results for the removal of fluoride. The uptake

of fluoride is possible in the range of pH 2 to 10, adsorption reached maximum

at lower water pH of 2. Hence, it is preferable to carry out defluoridation at

17
lower value of pH. From the present study, it is observed that fluoride removal

for adsorbent increases with time attaining equilibrium within 1 to 1.5 hours.

Adsorption of fluoride in aqueous solutions using KMnO4-modified

activated carbon derived from steam pyrolysis of rice straw

A.A.M. Daifullah, S.M. Yakout∗, S.A. Elreefy

Fluoride in drinking water above permissible levels is responsible for

human and skeletal fluorosis. In this study, activated carbons (AC) prepare by

one-step steam pyrolysis of rice strawat 550, 650, 750 ◦C, respectively, were

modified by liquid-phase oxidation usingHNO3, H2O2

andKMnO4.Characterization of these 12 carbons was made by their surface

area, porosity, acidity, basicity, PH, and ability to remove fluoride anion.

Based on the data of the latter factor, the RS2/KMnO4 carbon was selected.

Along with batch adsorption studies, which involve effect of pH, adsorbate

concentration, adsorbent dosage, contact time, temperature, and Co-ions

(SO42−, Cl−, Br−). The effects of natural organic matter (NOM) were also

made to remove the fluoride from natural water. On the basis of kinetic studies,

specific rate constants involved in the adsorption process using RS2/KMnO4

carbon was calculated and second-order adsorption kinetics was observed.

Equation isotherms such as Langmuir (L), Freundlich (F), Langmuir–

Freundlich (LF) and Dubinin –Radushkevich (DR) were successfully used to

model the experimental data.

18
A comparative study on the batch performance of fluoride adsorption by

activated silica gel and activated rice husk ash

Naba Kr Mondal1, Ria Bhaumik2,

A comparative study was done for removal of fluoride by activated

silica gel (ASiG) and activated rice husk ash (ARHA) through batch

techniques. The fluoride removal performance of both adsorbents such as

ASiG and ARHA was evaluated as a function of the initial

concentration, adsorbent dose, contact time and pH. The adsorbent dose

characterized as having high selectivity for fluoride and larger adsorption

capacity .Characterization of ASiG and ARHA before and after fluoride

adsorption was studied by SEM and FTIR study was done to get a better

insight into the mechanism of adsorption. The rate of adsorption was rapid

and followed pseudo-second-order kinetics for both adsorbents. The system

followed the Langmuir isotherm model for both ASIG and ARHA with

adsorption capacity 0.244 mg g-1 and 0.402 mg g-1 respectively.

In this study the ability of ARHA and ASIG to remove fluoride from

aqueous solution was investigated. The operational parameters such as pH,

initial fluoride concentration, adsorbent dose and contact time were found to

have an effect on the adsorption efficiency of ARHA and ASIG. The

maximum adsorption of fluoride was found at pH 2.0 for both the adsorbent.

According to Langmuir model the maximum adsorption capacity was

found in case of ARHA and ASIG were 0.402 mg/g and 0.244 mg-1

19
respectively. The equilibrium was attained at 100 minutes for both the

adsorbents, but percentage of removal was 88.30 and 96.7 for ARHA

and ASIG respectively. Further the adsorbent ARHA was characterized by

Fourier.

Effective Low Cost Adsorbents for Removal of Fluoride from Water:

A Review KoteswaraRao M1, Mallikarjun Metre 2

Drinking water contamination by fluoride is recognized as a major public

health problem in many parts of the world. In fact, although fluoride is an

essential trace element for animals and humans, excessive fluoride intake may

cause adverse health effects. The present survey highlights on efficiency of

different materials for the removal of fluoride from water. The most important

results of extensive studies on various key factors (pH, agitation time, initial

fluoride concentration, temperature, particle size, surface area,presence and

nature of counter ions and solvent dose) fluctuate fluoride removal capacity of

materials are reviewed. This paper investigates the potential health risks

involved with both lower and higher concentrations of fluoride in drinking

water, as well as posing possible measures of mitigation to eliminate such

harmful threats. Also, this paper describes brief discussions on various low

cost adsorbents used for the effective removal of fluoride from water. This

paper provides an overview of various low cost adsorbents used for the

effective removal of fluoride from water. Most of the adsorbents performance

is depend on the pH and temperature. The removal capacity increases by

20
increasing dose of the adsorbent and decreasing size of the adsorbent. The new

treated adsorbents are also available and hope that it will encourage even more

rapid and extensive developments for the treatment of fluoride.

Fluoride Removal from Drinking Water Using Used Tea Leaves as

Adsorbent S. JENISH1,* and P. AMAL METHODIS2

Fluoride concentration in drinking water above 1.5 ppm creates health hazards.

In the present investigation the removal of fluoride has been attempted using

used tea leaves obtained from college canteen. Characterization studies of used

tea leaves were carried out by standard procedures (ISI 1989 and APHA 1995).

Used tea leaves were treated chemically and digested in alum. The fluoride

removal studies were done by adsorption method on used tea leaves. The

effects of contact time, pH and adsorbent dose were investigated. The fluoride

removal process confirms to second order kinetics. The adsorption followed

Langmuir isotherm. The results show that the adsorption capacity of the

adsorbent used tea leaves was found to be 0.253 mg/g. Regeneration is

effective using 2 % alum solution in the column.

Effective Low Cost Adsorbents for Removal of Fluoride from Water

Sheetal Bandewar1, S. J. Mane2, S. N. Tirthakar3

Millions of people rely on drinking water that contains excess fluoride. In

fluoride endemic areas, especially small communities with staggered habitat,

defluoridation of potable water supply is still a problem. In this study,

adsorption potential of granular activated carbon (GAC) from charcoal and

21
coconut shell is investigated for defluoridation of drinking water

usingcontinuous fixed bed column. The influence of various operative

parameters such as concentration of fluoride, bed height, flow rate, and

adsorption capacity of both the adsorbent is carried out.The fluoride removal

from synthetic sample is found up to 72% for fluoride ion concentration of

4mg/L

. Removal of fluoride from aqueous solution by using low cost adsorbent

PaliShahjee1, B.J.Godboley2, A.M.Sudame3

Fluoride contamination in drinking water due to natural and anthropogenic

activities has been recognized as one of the major issue imposing a serious

threat to human health. Among several treatment technologies applied

forfluoride removal, adsorption process has been explored widely and offers

satisfactory results, so objective of this study was to investigate or check

efficiency of low cost adsorbent (Bleaching Powder) for the removal of excess

fluoride from aqueous solution. The influence of various operational

parameters viz. effect of adsorbent dose, pH, initial concentration and contact

time were studied by a series of batch adsorption experiments. 7.3gm/100ml

(0.7mg/l is the new limit of fluoride according to EPA & HSS) was calculated

as optimum dose of adsorbent. It was noticed that adsorbent is showing a good

efficiency between 6-10 pH. In contact time variation it was noticed that it

show rapid adsorption of Fluoride from 4 to 7 hr, thereafter, the adsorption rate

gradually reaches equilibrium in 8hr-9hr. These conditions make it very

22
suitable for use in drinking water treatment. From these studies, it may be

concluded that bleaching powder is an efficient and economical adsorbent for

fluoride removal from aqueous solutions.

Investigation on Sorption of Fluoride in Water Using Rice Husk as an

Adsorbent Waheed S. Deshmukh, S. J. Attar andM. D. Waghmar

The batch adsorption studies were undertaken to assess the suitability of

inexpensive adsorbent prepared from agricultural waste, rice husk. The

adsorbent was prepared by chemical impregnation method followed by

physical activation. Static studies have aimed for investigation of fluoride

removal efficiency under the varying conditions of the major parameters of

adsorption, viz. pH, dose of adsorbent, rate of stirring, contact time and initial

adsorbate concentration, and optimized by batch procedure in themixture of

known concentration of fluoride solution. The optimum sorbent dose was

found to be 10g/L by varying the dose of adsorbent from0 to 16g/L;

equilibriumwas achieved in 120 min for the optimum pH. It has been observed

that the optimum adsorption takes place at lower pH by varying pH from 2, 4,

6, 8, 10. Maximum fluoride removal was observed to be 75% at optimum

conditions. Freundlich as well as Langmuir isotherms were plotted and

constants of isotherms were determined.

23
Removal Of Fluoride From Water And WasteWater By Using Low Cost

AdsorbentsN. Gandhi1*, D. Sirisha1, K.B. Chandra Shekar2 and Smita

Asthana3

India is among 23 nations where in a large population suffers from dental and

skeletal flourosis due to high fluoride concentration in ground water. The

prominent states, which are severely affected, are Andhra pradesh, Rajasthan,

Gujarat, Uttar Pradesh and Tamil Nadu. Fluoride beyond desirable amounts

(0.6to 1.5 mg/l) in ground water is a major problem in many parts of the world.

Taking the severity of theproblem into consideration, the present study is

carried out to study on effective and cheap adsorbents forthe removal of

fluoride from the water. Batch adsorption studies are carried out. Batch

adsorption studiesdemonstrate that the adsorbents have the significant capacity

to adsorb the Fluoride from water. Theexperiments were carried out in

laboratory on certain low cost adsorbents like concrete, ragi seed powder,Red

soil, horse gram seed powder, orange peel powder, chalk powder, pineapple

peel powder and multhanimatti.

24
 CHAPTER: 3

MATERIAL COLLECTION & PROPERTIES

Water sample map

The figure illustrates the water sample map. It is nothing but, the school

located villages and fluoride hazardous areas water sample was collected to

fluoride analysis. So this water sample collected areas are shown in figure

water samples are collected from BOOTHAKUDI, CHINTHAMANI,

MELUR, KULAMANGALAM

Fig 3.1 Water sample collection map

25
Water Sample Collection

Field data consist the processes of ground water sample collections,

chemical analysis, and data interpretation. In this study ground water has been

taken and analysed for fluoride (f-).the fluoride hazardous zones were

identified from the dental fluorosis survey. The fluorosis affected students

natives are considered as fluoriode hazardous zone .so that areas drinking

water source is taken and test is taken in laboratory .The result depends upon

the present ground station conditions from this dental survey result I find the

fluoride hazardous zones at Madurai north block. there are

➢ Chinthamani
➢ Boothakudi fig 3.2.water sample collection

➢ Kulamangalam

➢ melur

Dental fluorosis survey report prepared in ThylstrupFrejeskovintex (1998)

form.ThylstruptFrejeskovintex give of affection like mild, moderate, severe

depend on the score value. The score value of ThylstrupFrejeskov index table

is given below. The hazardous report of this project is carried out with

ThylstrupFrejekov index. Because it is easy method to identify the students as

per the affection.ThylstrupFrejeskov index is helps to differentiate the fluorosis

affected students like very mild, mild, moderate and severely.

26
 Table 3.1 ThylstrupFrejeskov Index

SCORE CRITERIA
0 Nil
1 and 2 Very Mild
3 Mild
4 Moderate

Ricehusk and moringaolifera seeds

Rice husk contains abundant floristic fiber, protein and some functional

Groups such as carboxyl, hydroxy and amidogen, etc. which makes adsorption

processes possible (Runping Han, et al. [10]) Moringa oleiferaconsists

chemical compounds like 4-(4'-O-acetyl-a-L-rhamnopyranosyloxy) benzyl

isothiocyanate, 4-(a-L-rhamnopyranosyloxy) benzyl isothiocyanate,

niazimicin, pterygospermin, benzyl isothiocyanate, and 4-(a-L-

rhamnopyranosyloxy) benzyl glucosinolate and several studies reported on the

performance of Moringa oleifera seeds as a primary coagulant, coagulant aid

and conjunctive with alum (Jed [11]).

The objective of the present study is to investigate the effectiveness of

naturally occurring and low-cost materials like Rice Husk and Moringa olifer

aand chemicals like Manganese chloride and Manganese sulphate for removal

of Fluorides from water.

27
Table 3.2 Composition of rice husk ash on dry basis
Physical properties/chemical
composition Values

Average particle size 150.47

Bulk density 104.9 kg/m3

Heating value 9.86 MJ/kg

BET surface area 34.44m2/g

Average pore diameter by BET 42.603 0A

PHZPC 6.0

Silica(SiO2) 80-90%

Alumina 1-2.5%

Ferric acid 0.5%

Titanium dioxide Nil

Calcium oxide 1-2%

Magnesium oxide 0.5-2.0%

Sodium 0.2-0.5%

Potash 0.2%

28
 CHAPTER:4

EXPERIMENTAL METHODOLOGY

4.1 Materials: Corning glassware of ‘Pyrex’ quality and analytical reagent

grade chemicals were used. The glassware was soaked overnight in a 5.0 mg/L

of Fluoride solution to minimize the possibility of Fluoride getting absorbed.

The glassware was washed off with nitric acid and distilled water before use.

First, a stock solution of 100 mg F/L was prepared by dissolving appropriate

amount of sodium fluoride (NaF) in distilled water and desired concentrations

of working solutions were then prepared from stock solution. Sulphuric acid

(0.1N) and sodium hydroxide (0.1 N) were used for adjusting the pH values

either to acidic or alkaline conditions.

Naturally occurring and abundantly available low cost materials like Rice

husk, Moringa Oleifera seeds were used. Rice husk was obtained from a local

mill and was sieved through IS sieves of 150 μm and 300 μm size and the

material passing through 150 μm and retained on 300 μm which has a

geometric mean size (Gm) of 212 μm was used in all experiments. The

apparent density of rice husk is 0.4-0.7 g/cm3.

Dried Moringa Oleifera seeds were obtained locally and kept in an oven 500C

for 12 hrs. The seeds were made into powder and sieved through 75 μ sieve to

get uniform size. In order to obtain an extract of Moringa Oleifer and powder

first 10 g of Moringa powder Observed visually for dissolution of Moringa

Oleifera powder. It was observed that 0.5N HCI was more effective in

29
dissolving Moringa Oleifera powder.

Methodology

Agitated, non-flow batch sorption studies were conducted to study the effect

of controlling parameters like contact time, sorbent dosage, solution pH etc.

Continuous down flow column studies were also conducted to study the

practical applicability of rice husk for removal of Fluorides from water. All the

experiments were conducted at room temperature (29±20C). Fluoride

concentration was estimated by SPADNS method (APHA[12]) using a

SYSTRONICS-105 spectrophotometer.

Selection of adsorbent

To select a suitable defluoridation method following criteria need to be

considered:

• Fluoride removal capacity

• Simple design

• Easy availability of required materials and chemicals

• Acceptability of the method by users with respect to taste and cost

fig.3.3 Rice husk, seed and sand

30
Table 4.1: Merits and Demerits of some Defluoridation methods

METHODS MERITS DEMERITS ESTIMATED

RELATIVE
Nalgonda Low technology, 1. Large quantity of Low – media
adaptable at point of sludge.
use & point of source 2. High chemical
level dose.
3. Dose depend on F-
level
4. Daily addition of
chemicals and
tirring in point of
source units
Bone Char Local available 1. May impart Low –
media taste and odour and media
result in organic
leaching if not
prepared properly
2. Requires
regeneration
periodically
3. Effected by high
alkalinity
4. May not be
acceptable
Activated Effective, much 1. Periodic Medium –
Alumina experience regeneration. High
2. Skilled personnel
for plant operation.
3. Properly trained.
staff for regeneration
of point of use units.
Suitable grades may
not be indigenously
available in less
developed countries.
Contact Not much experience 1.Algal growth can High –
precipitation occur in phosphate Very high
solution
2. Bone char used as

31
 a catalyst may not be
acceptable in many
countries.
Brick Low cost May not be High –
High – technology universally Very high
Very high applicable

Reverse Can remove 1.Skilled operation Very High

osmosis other ions 2. Interference by
turbidity
3. High cost

32
4.2 Fixed-Bed Column Studies

The sorption studies are carried out in a glass column of 2.5 cm diameter and

bed height of 25 cm. Four sets of column study are performed. A glass-wool

plug is used in the bottom of the column to support the adsorbent bed and

prevent the outflow of particles. In each set, for a given initial fluoride

concentrations (2, 4, 6 and 8 mg/L) the downward flow rates are varied and

maintained at (2 ml/min, 4ml/min, 6ml/min, and 8ml/min) corresponding to

each of the various concentration values. The GAC of both the material is

filled in the glass column in equal amount as 3+3cm. The top of the column is

connected to an overhead tank containing the feed solution. The effluent is

collected and analyzed for fluoride concentration. Packed bed experiments

carried out at roomtemperature.carried out at room temperature.

fi

fig. 3.4column with rice husk and seed

33
 CHAPTER: 5

RESULTS AND DISCUSSIONS

5.1 Effect of Bed Height

For optimization of adsorbent depth, the columns are filled with an

increment of 2 cm in all four columns subsequently. The depth which gives

maximum removal is the optimum bed depth. Accumulation of F ion in the

fixed bed column is largely dependent on quantity of absorbent inside the

column. It is observed that the removal of fluoride ion increases with an

increase in the amount of adsorbent up to 6 cm depth thereafter it shows little

decrease or remains constant. In present study the maximum fluoride removal

has take place at 6 cm bed height and results are shown in fig.

34
5.2 Effect of Flow Rate

For optimization of flow rate the optimized bed height 6 cm is kept constant.

Flow rate is adjusted to 2 ml/min, 4ml/min, 6ml/min, and 8ml/min in four

columns. The flow rate which gives maximum removal of fluoride ion is the

optimum flow rate. It is observed that the removal of fluoride increases with

increase in contact time to some extent. Further increase in flow rate does not

increase the fluoride removal efficiency. This rapid initial increase in

adsorption subsequently gives the way to a very slow approach to equilibrium

and saturation is reached at flow rate 4 ml/min.

The results are shown in fig. 2.

35
5.3 Final Analysis

Final analysis is carried out by using synthetic sample of 4mg/l fluoride

concentration and using above optimized parameters i.e. bed depth = 6cm and

flow rate = 4ml/min at normal temperature is kept constant and analyzed over

single column. Finally by using both the adsorbent in equal quantity (granular

charcoal activated carbon and granular coconut shell activated carbon) proved

that it can efficiently remove 74% of fluoride from drinking water.

Table 5.1 Fluoride removal efficiency at initial conc. 4 mg/l

S.NO Flow rate Adsorbent Initial conc. = 4 mg/l
dose
Removal mg/l Efficiency %
1 2ml / min 3cm+3cm 1.09 27.25

2 4ml / min 3cm+3cm 1.89 47.45

3 6ml / min 3cm+3cm 2.85 71.25

4 8ml / min 3cm+3cm 2.97 74.25

36
80

70

60

50

40
Series1
30

20

10

0
2ml/min 4ml/min 6ml/min 8ml/min

37
Table 4.2Fluoride removal efficiency at initial conc. 9 mg/l

S.NO Flow rate Adsorbent Initial

dose Conc.=9mg/l

Removal mg/l Efficiency %

1 2ml/min 3cm 3.67 40.77

2 4ml/min 3cm 4.56 50.66

3 6ml/min 3cm 5.98 66.44

4 8ml/min 3cm 6.08 67.55

80

70

60

50

40
Series1
30

20

10

0
2ml/min 4ml/min 6ml/min 8ml/min

38
Table 5.3Fluoride removal efficiency at initial conc. 5 mg/l

S.NO Flow rate Adsorbent Initial

dose Conc.=5mg/l
Removal mg/l Efficiency %

1 2ml/min 3cm 1.09 21.8

2 4ml/min 3cm 1.86 37.2

3 6ml/min 3cm 2.30 46
4 8ml/min 3cm 2.45 49

60

50

40

30
Series1

20

10

0
2ml/min 4ml/min 6ml/min 8ml/min

39
 6.CONCLUSION

The experimental investigations clearly suggest that abundantly available

andlow-cost materials like Rice Husk, seed extracts of Moringa Oleifera

(Drumstick) and chemicals like Manganese Sulphate and Manganese Chloride

areeffective in removing Fluoride from water to acceptable levels.

Equilibriumisothermal sorption experiments suggested that sorbent dosages of

6g/l of ricehusk accomplished a removal of 74.25% of Fluoride. The time to

reach equilibriumwas observed to be 3 hours. pH does not have any significant

impact in the range of 3-10, where as pH of more than 10 resulted in a steep

decrease in Fluoride removal. Manganese Sulphate, Manganese Chloride

exhibited good percentage removal of Fluoride. Acid extract of natural

Polyelectrolyte Moringa Oleifera seed is very effective as a coagulant for

removal of Fluoride. A dose of 1000 mg/l removed 74.25% of Fluoride.

40
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43