TOXICITY of

FLOURIDES
AND
DEFLOURIDATION
of WATER
CONTENTS:
Toxicity of Fluorides:
1. Introduction
2. Acute Toxicity
3. Chronic toxicity
– Dental fluorosis
– Skeletal fluorosis
4. Other deleterious effects of fluoride
ingestion
5. Effects of NaF at molecular level
6. Management of Fluoride toxicity
Defluoridation of Water:
1. Introduction
2. Methods of defluoridation
– Adsorption technique of defluoridation
– Ion exchange resins
– Precipitation technique -Nalgonda technique
• Mechanism of action
• Maintenance
• Indications
• Merits and Demerits
• Modifications
– Other techniques
Conclusion
TOXICITY OF
FLOURIDES
Introduction
 Fluoride occurs naturally in our environment
but we consume it in small amounts.
 Exposure can occur through dietary intake,
respiration and fluoride supplements.
 The most important factor for fluoride
presence in alimentation is fluoridated water.
 Fluorides are toxic compounds that may be
lethal if ingested in dose exceeds 15mg/kg body
weight. Due to its reactivity, fluoride may be
cytocidal by inactivating cell enzymes, such as
the enolase metabolism of the cells
 Today, poisoning is mainly due to
unsupervised ingestion of products for
dental and oral hygiene and over-
fluoridated water.
 It is involved in chronic and acute fluorosis.
Chronic side effects are found in
mineralized tissues, leading to dental or
skeletal fluorosis, depending on the dose.
Acute effects range from gastrointestinal
symptoms to death
Certainly lethal dose: 32-64 mg/kg body wt.
Safely tolerated dose: 8-16 mg/kg body wt.
 Acute Fluoride toxicity
 When sufficient large amount of fluoride are ingested
as a single dose, a catastrophic chain of event rapidly
develops. The first effects experienced by the victim
usually include nausea, vomiting, and burning or
cramp like abdominal pains.
 These symptoms are caused due to fluoride combining
with the gastric juices to form excessive HCl.
 There may be excessive salivation and tearing, mucous
discharges from the nose and mouth, a generalized
weakness, paralysis of muscles of swallowing, crapo-
pedal spasm or spasm of the extremities, tetany, and
generalized convulsions.
 The pulse may be thready or not detectable.
 Blood pressure often falls to dangerously low levels at
some point during the course of the toxic episode.
 As respiration is depressed a respiratory acidosis
develops.
 After 2-4 hours fatality is possible if first aid is not
administered.
 Death maybe caused by blockade of normal cellular
metabolism causing cardiac failure and respiratory
paralysis.
 If death hast occurred within 24 hours , prognosis is
good.
 The different chemical forms of fluoride vary in their
toxic potentials as well, chiefly because of differences
in the rate or degree of absorption from GI tract.
 Studies have shown that younger animals are more
resistant to the lethal effects of fluoride.
 Chronic Fluoride toxicity
 As mentioned earlier, chronic side effects are
found in mineralized tissues, leading to dental or
skeletal fluorosis, depending on the dose.
 Results from long term ingestion of small
amounts of fluorides.
 A. DENTAL FLUORISIS
 Dental fluorosis occurs as a result of excess
fluoride ingestion during tooth formation.
Enamel fluorosis and primary dentin fluorosis can
only occur when teeth are forming, and therefore
fluoride exposure occurs during childhood.
 Ingestion of water with fluoride concentration of
2X- 3X greater than recommended amounts
causes white flecks and chalky opaque areas on
tooth enamel.(mild fluorosis)
 Ingestion of water with fluoride concentration of
4X greater than recommended amounts causes
brown pitted or corroded surface of enamel.
 However these teeth are highly resilient to
carious attack.
B. SKELETAL FLUORISIS
 Results from ingestion of very high amounts of
fluorides for long periods of time.
 At water fluoride levels above 8 ppm, skeletal
fluorosis may develop.
 In India, it was first reported by
Vishvanathan(1935) in Madras Presidency in
1933.
 Symptoms include:
 Severe pain and stiffness in backbones, spine and
hips
  Outward bending of hands and legs are seen in
advanced stages and these parts loose their shape
and contours.(KNOCK KNEE SYNDROME)
 Pregnant lactating mothers and children are more
vulnerable group. It damages fetus if taken in
excess.(CaF2 more toxic to fetus than NaF).
 It may lead to blocking and calcification of blood
vessels causing cardiac problems.
 SEVEREST- CRIPPLING FLUORISIS, spine
becomes rigid and the joints stiffen, virtually
immobilizing the patient.
 Neurological manifestations- ADVANCED

MAXIMUM DOSE :20-80 mg/day for 10-20 years.

 Concentrations of fluoride in drinking water are
related to caries incidence in children and
severity of dental fluorosis. Adapted from a
report of the Department of Health and Human
Services of US (1991)
Other deleterious effects
of fluoride ingestion:

 A review of brain studies involving the use of fluoride

has concluded that one of the adverse effects of
fluoride exposure on children is damage to their
neurological development.
 According to the Harvard researchers, children who
lived in high-fluoride areas had “significantly lower
IQ than those in low fluoride areas”
 There have been over 23 human studies
and 100 animal studies linking fluoride to
brain damage

Effects of NaF at molecular

level
 Induces cell proliferation via BMP pathway
during skeletal fluorosis.
 High fluoride levels causes hindrance in cell
proliferation growth.
 Fluoride induces G0/G1 arrest, apoptosis
and DNA damage.
 MANAGEMENT OF ACUTE
FLUORIDE TOXICITY
 IF INGESTED FLUORIDE <5mg/kg body weight:
 Give calcium orally (milk) to relieve gastro-
intestinal symptoms.
 Induce vomiting (may not be necessary).
 IF INGESTED FLUORIDE >5mg/kg but
<15mg/kg body weight:
 Empty the stomach by inducing vomiting with
emetic. For patients with depressed gag reflex,
inducing vomiting is contraindicated and
endotracheal intubation should be performed
before gastric lavage.
  Give orally soluble calcium in any form- milk; 5%
calcium gluconate or calcium lactate solution.
 Admit to hospital and observe.
• IF INGESTED FLUORIDE >15mg/kg body weight:
 Admit to hospital immediately.
 Induce vomiting.
 Begin cardiac monitoring.
 10ml of 10% calcium gluconate slow IV; additional
doses if clinical signs of tetany develops. Electrolytes
especially Calcium and Potassium should be
monitored.
 Adequate urine output to be maintained, using
diuretics if necessary.
 General supportive measures of shock.
DEFLOURIDATION

OF

WATER
 Deflouridation of water is the process of
removing excess naturally occurring fluoride
from drinking water in order to reduce
prevalence and severity of fluorosis.
 It is defined as “the downward adjustment of
level of fluoride in drinking water to the optimal
level”.
 It is part of the National Programme for provision
of safe drinking water.
 The 1984 WHO guidelines suggested that in
areas with a warm climate the optimal fluoride
concentration in drinking water should remain
below 1 mg/l (1ppm or part per million), while in
cooler climates it could go up to 1.2 mg/l.
 Optimum fluoride concentration in drinking
water may be defined as “the one that can
arrest the prevalence of dental caries while
causing a insignificant amount of fluorosis”
 The highest fluoride concentration ever
found in natural water was 2800 mg/l,
recorded in Lake Nakuru in the Rift valley in
Kenya.
 15 of India's 32 states and union territories
were identified by UNICEF as endemic for
fluorosis
Methods of defluoridation
 Most obvious method being- change water
supply to one containing acceptable levels of
fluorides.
 Other methods involve chemical and
physicochemical methods of removal of
fluorides.
 These methods are broadly divided into:
A. Adsorption technique
B. Ion-exchange resins
C. Precipitation technique
D. Other techniques, which include electro
chemical defluoridation and Reverse
Osmosis.
 Adsorption technique of
defluoridation
 This technique functions on the adsorption of
fluoride ions onto the surface of an active
agent.
 Activated alumina, activated carbon and bone
char were among the highly tested adsorbing
agents.
 A. Activated Alumina:
 Application of domestic defluoridation plant, based
on activated alumina, was launched by UNICEF in
rural India
The disadvantages with activated alumina are:
 Adsorption of fluoride is possible only at specific pH
range, needing pre and post- pH adjustment of water.
 Frequent activation of Alumina is needed, which
make the technique expensive
 B. Bone char :
The process of Defluoridation by bone char as
the ion exchange and adsorption between
fluoride in the solution.
The efficacy of the plant depends upon
temperature and pH of raw water; duration for
which the bone-char is in contact with raw
water. It is a highly economic technique with a
defluoridation percentage of 62 to 66.
Disadvantage :
 The bone char harbors bacteria and hence unhygienic.
 It is a technique sensitive procedure,
 The use of bone-char may invite cultural and religious
objections
 Brick pieces column:
 The basic principle of functioning of Brick piece column is
the same as that of activated alumina.
 The soil used for brick manufacturing contains Aluminum
oxide.
 Mud pot :
The fluoride removal capacity will vary with respect to the
alumina content .
The major advantages of mud pots are they are economic
and readily acceptable for the rural communities .
 Natural adsorbents :
Many natural adsorbents from various trees were tried as
defluoridation agents- Seeds of the Drumstick tree, roots
of Vetiver grass and Tamarind seeds were few among
them.
Researchers at “M. S. Swaminathan Research Foundation‟
(MSSRF) had shown drumstick seeds to have remarkable
defluoridation efficiency, which was higher than that of
activated alumina.
 Ion exchange resins
 These are commercially produced resins which
are expensive and uneconomical in most
circumstances.
1. CARBION- cation exchange resin of good
durability, used on Na and H cycles.
2. DEFLUORON 1- sulphonated sawdust
impregnated with 2% alum solution.
3. DEFLUORON 2- (1968) sulphonated coal
using aluminum solution as regenerant.
Although it was successful in removing
fluorides, regeneration and maintenance of
the plant required skill.
Drawbacks of Ion-exchange
and adsorption techniques:
1. The necessary flow through system is often difficult
to arrange where there is no piped water supply.
2. Gradual exhaustion of the active agent is not easily
detected.

Precipitation technique
 Precipitation methods are based on the addition
of chemicals (coagulants and coagulant aids) and
the subsequent precipitation of a sparingly
soluble fluoride salt as insoluble fluorapatite
 The best example for this technique is the
famous Nalgonda technique of defluoridation.
 Nalgonda Technique
 Developed by the National Environmental
Engineering Research Institute (NEERI), Nagpur
in 1974 by Nawlakhe et al, reported by Bulusu in
1988.
 Method:
 Raw water is mixed with sodium
aluminate(filter alum), lime and bleaching
powder. If the raw water has adequate
alkalinity, the addition of lime is not required.
 This is followed by flocculation, sedimentation
and filtration.
 This technique is useful in both domestic as well
as for community water supplies.
 Mechanism:
 Unit hold 22 liters of water which is filled into
the upper chamber.
 Rapid mix:
◦ This is an operation by which the coagulant is
rapidly dispersed uniformly throughout a single
and multiple phase system.
◦ Rapidly mixed for 30-30 s with speed of 10-20 rpm.
◦ This helps in formation of microflocs and results in
proper utilization of chemical coagulant
preventing localization of concentration and
premature formation of hydroxides which may
lead to reduced utilization of coagulants.
 Flocculation:
◦ It is 2nd stage of formation of settable
particles(flocs) from destabilized colloidal sized
particles and is achieved by gentle and
prolonged mixing for a period of 10-15 min with
speed of 2-4 rpm.
 Sedimentation:
◦ It is separation of water by gravitational
settling of suspended particles that are heavier
than water.
◦ Factors that influence sedimentation:
1. Size, shape, density and nature of the particles.
2. Viscosity density and temperature of water.
3. Surface overflow rate.
4. Velocity of flow
5. Effective depth of settling zone.
 Filtration:
◦ It is process of separating suspended and
colloidal impurities from water by passage
through a porous media. The flocculated water is
alowed to settle and filtered through fullers earth
candles overnight.
 Treated water level of fluoride: 1ppm
 Maintenance of filters:
 The package plant installed on handpump
schemes costing 1.6 lacs to serve 250
population requires skilled operator and
chemicals for treatment; 50 stainless steel
filters are required costing Rs. 35,00,000.
 Major advantage would be low cost of
investment and maintenance.
Merits:
 It can be used both at domestic and
community levels.
 Operations are possible manually.
 The chemicals are the same as those used in
municipal/urban water supply schemes.
 It is cost effective.
 There is considerable flexibility in design,
construction operations and maintenance,
therefore location specific alterations are
possible.
 Even effective when dissolved solids are
above 1500mg/l and hardness above
600mg/litre.
 Defluoridated water meets with the
standards laid down by the Bureau Indian
Standards, that is, the fluoride content in
water shall be lower than 1 ppm.
 Readily available chemicals are being
used.
 Highly effective
 Less wastage of water.
 Needs minimum mechanical and electrical
equipment
 No energy except muscle power for
domestic equipment.
Drawbacks
 No regeneration of media.
 Doses of alum and lime are determined after assessing
the fluoride content and alkalinity of the raw water.
 Generation of higher quantity of sludge compared to
electrochemical defluoridation
 The large amount of alum needed to remove fluoride.
 It is mandatory that this dose is re-assessed during
extreme summer and in the rainy season, when fluoride
concentration and alkalinity of the water can alter.
 Technique sensitive, if the alum mixing is carried out at
a greater velocity there are less chances of floc
formation and a greater quantity alum will be required
for removal fluoride which may result in residual Al in
 The major cause for concern is that if the dose of alum
is not altered to need there is a possibility of excess
aluminum contaminating the water; excess is suspected
to cause Alzheimer‘s disease.
(The maximum contamination of aluminum permitted is
0.03 mg - 0.2 mg/litre of water according to B1S.)

Indications
 Absence of acceptable, alternate low fluoride source
within transportable distance.
 Total dissolved solids below:1500mg/l. Desalination nay
be necessary when the exceed 1500mg/l.
 Raw fluoride ranging from 20mg F/l
 Modifications for Nalgonda
technique.
 Poly Aluminum Chloride(PAC):
◦ It is evident that for higher concentrations of
fluoride, the removal efficiency of fluoride is
higher with Poly Aluminum Chloride (PAC)
when compared with Alum.
 Poly Aluminum Hydroxy Sulphate(PAHS):
◦ A polymeric aluminum compound, poly-
aluminum hydroxy-sulphate(PAHS) is found to
require less flocculation time and settling time.
Domestic deflouridation
filters
 These are stainless steel candle filters adopting
the Nalgonda technique. The equipment consists
of water filter of any size and make, fitted with
candle filters and additional mixing device which
can be used as additional deflouridation filters.
 Nalgonda tech is simple and economical process
that can be adopted by the common man.
 It can be adopted both at domestic and
community level.
 Both fill and draw and continuous operation
system can be installed for deflouridation of
water at community water supply.
Other techniques of
defluoridation
 Reverse osmosis, electrolysis and electro
dialysis are physical methods that are tested
for defluoridation of water.
 Though they are effective in removing
fluoride salts from water, there are certain
disadvantages that limit their usage on a large
scale.
 Both processes are very complicated
 Reverse Osmosis :
◦ In reverse osmosis, the hydraulic pressure is
exerted on one side of the semi permeable
membrane which forces the water across the
membrane leaving the salts behind.
 Electro dialysis
◦ In electro dialysis, the membranes allow the
ions to pass but not the water. The driving
force is an electric current which carries the
ions through the membranes
◦ Electro dialysis is highly energy intensive and
expensive.
 Defluoridation by electrolysis:
◦ The basic principle of the process is the
adsorption of fluoride with freshly precipitated
aluminum hydroxide, which is generated by
the anodic dissolution of aluminum or its
alloys in an electro chemical cell.
Advantages of using newer
techniques:
 Does not require addition of chemicals.
 No need to pre & post-treatments .
 Low volume of sludge.
 Units can be designed for any capacity.
 Units are designed for specific locations &
fluoride content of water. But can be operated
with varying fluoride concentrations by slightly
altering the operating parameters.
 The electrochemical reactor occupies less floor
space.
 Operator friendly
 Requires less electric energy (0.3 to 0.6kwh/1000
liters)
 Conclusion
 Fluorosis is an important public health problem in
India.
 Drinking water is the main source of ingestion of
fluoride.
 There is no cure to the disease and prevention is
the only solution.
 Nalgonda technique is the most suitable technique
for Indian rural communities.
 Communities should be educated and encouraged
to actively participate in the procedure.
 Suitable technique for the community should be
identified.
 Priority should be given to techniques, which utilize
locally available materials as defluoridation agents.
THANK
YOU