Defluoridation TechniQues

-To Enhance The Human Life Better.

Abstract:

The universal solvent, water is a natural resource for sustaining life. Though water is
available in abundance and a free gift of nature, chemical composition of surface or
subsurface, geothermal or non – thermal of the region are the prime factors on which the
suitability of the water for domestic, industrial or agriculture purpose depends. Most of
the population in India is illiterate and not aware of water born diseases. Major problems
being faced in certain parts of the country are due to the presence of excess fluoride,
arsenic and nitrate contents in groundwater .The 1984 WHO guidelines suggested an
optimum value for fluorine in drinking water should be 1.5mg / litre. Fluoride at lower
levels causes dental cavities while poisonous at higher levels causing dental fluorosis,
skeletal damage. This paper provides a literary review on the latest physical and chemical
fluoride removal techniques employed world wide for optimum removal in drinking
water. An attempt is made on reviewing comparative study on de-fluorination techniques
by impregnation of metal ions such as ZrOCl2, CaO, Alum , CaCl2 and Borax in
activated charcoal suggesting the most promising techniques. Global scenario of fluoride
removal techniques and various health hazards are also presented.

Key words: Defluoridation, fluorosis, nalgonda technique, Activated alumina, Zirconium

ion.

Introduction:

Fluorine is the most highly reactive element of the halogen family. It exists in water
mainly as fluoride ion. Fluoride has been described as more toxic than lead and less toxic
than arsenic and is considered as an accumulative toxin.. Fluoride has dual significance.
If the fluoride content is less, then it may cause problems like dental cavities. W.H.O has
stated that it should be in the range of 0.1 to 0.5ppm. By U.S. standard, the fluoride
content in water should be between 0.6 and 0.9ppm. The Indian Standard for fluoride
contents is 1 ppm. This shows that the requirement of fluoride content changes, and it
depends on the geographical condition and the age of human beings. High-fluoride
ground waters are found in many parts of the developing world, and many millions of
people rely on groundwater with concentrations above the WHO guideline value. The
latest information shows that fluorosis -a serious bone disease is endemic in at least 25
countries across the globe. In the early 1980s, it was estimated that around 260 million
people worldwide (in 30 countries) were drinking water with more than 1 mg/l of
fluoride. In India alone, endemic fluorosis is thought to affect around 1 million people
and is a major problem in 17 out of the country’s 22 states, especially Rajastan, Andra
Pradesh, Tamil Nadu, Gujarat and Uttar
Pradesh. To date, only 14% of rural and 70% of urban inhabitants have access to
adequate sanitation facilities. Fluorosis is prevalent in some parts of central and western
China, and caused not only by drinking fluoride in groundwater but also by breathing
airborne fluoride released from the burning of fluoride-laden coal. Worldwide, such
instances of industrial fluorosis are on the rise.. The dominant controls on fluoride build-
up in water are:
i) geology;
ii) contact times with fluoride minerals;
iii) groundwater chemical composition;
iv) climate.

The most common fluorine-bearing minerals are fluorite, apatite and micas.

Sources of pollution:

Pollution of surface and groundwater resources occurs through point and diffuse sources.
Examples of point source pollution are effluents from industries, sewage-treatment plants
and untreated domestic sewage. The main sources of diffuse pollution may be
anthropogenic activities, such as agricultural applications of fertilizers and pesticides or
of geo-chemical origin, such as natural contamination of groundwater sources by
fluoride, arsenic and dissolved salts. The industries, which are burgeoning at a fast rate,
produce about 55,000 million m3 of wastewater per day, out of which 68.5 million m3 is
discharged into river and streams. Inadequate treatment of human and animal wastes
contributes to the high incidence of water-related diseases in the country.

Health effects:

We purposely fluoridate a range of everyday products, notably toothpaste and drinking

water, because for decades we have believed that fluoride in small doses has no adverse
effects on health to offset its proven benefits in preventing dental decay. According to
1984 guidelines published by the World Health Organization (WHO)1, fluoride is an
effective agent for preventing dental caries if taken in 'optimal' amounts. But a single
'optimal' level for daily intake cannot be agreed because the nutritional status of,
individuals, which varies greatly, influences the rate at which fluoride is absorbed by the
body. A diet poor in for example, increases the body's retention of fluoride. Water is a
major source of fluoride intake. The 1984 WHO guidelines suggested that in areas with a
warm climate, the optimal fluoride concentration in drinking water should remain below
1 mg/litre (1ppm or part per million), while in cooler climates it could go up to 1.2
mg/litre. The ingestion of large amounts of fluoride, whether via water or food, can
cause serious health problems for humans and animals. These range from discoloured
teeth (i.e. dental fluorosis) to aching joints, brittle bones, stunted growth and deformed
limbs (i.e. skeletal fluorosis). Non-skeletal fluorosis can also have severe symptoms.
These include gastro-intestinal problems and neurological disorders. Fluoride can damage
unborn babies and adversely affect the intelligence of children. As it can affect the pelvic
bones, pregnant women often have to undergo caesarean operations. Dental fluorosis,
which is characterized by discoloured, blackened, mottled or chalky-white teeth, is a
clear indication of overexposure to fluoride during childhood when the teeth were
developing. These effects are not apparent if the teeth were already fully grown prior to
the fluoride overexposure.

Better nutrition

Clinical data indicate that adequate calcium intake is clearly associated with a reduced
risk of dental fluorosis. Vitamin C may also safeguard against the risk. In consequence,
measures to improve the nutritional status of an affected population particularly children -
appear to be an effective supplement to the technical solutions discussed above.

Fluoride in drinking water mg/LEffects

Below 1.0safe
1..0-1.5marginal
1.5-3.0High risk of dental fluorosis
3.0-10.0Leads to skeletal fluorosis with adverse changes in bones
More than 10.0Crippling skeletal fluorosis

Defluoridation methods:

Defluoridation is removal of excess fluoride from water. Several methods have been
suggested for removing excessive fluoride in water. The defluoridation methods are
divided into three basic types depending upon the mode of action :

1. based on some kind of chemical reaction with fluoride

2. based on adsorption process
3. based on ion-exchange process

Based on chemical reaction

Nalgonda technique

The Nalogonda technique (named after the village in India where the method was
pioneered) employs flocculation principle . Nalgonda technique is a combination of
several unit operations and the process invloves rapid mixing, chemical interaction,
flocculation, sedimentation, filtration, disinfection and sludge concentration to recover
waters and aluminium salts. Alum (hydrated aluminium salts) - a coagulant commonly
used for water treatment is used to flocculate fluoride ions in the water. Since the process
is best carried out under alkaline conditions, lime is added. For the disinfection purpose
bleaching powder is added. After through stirring, the chemical elements coagulate into
flocs and settle down in the bottom
The reaction occurs through the following equations

2 Al2 (SO4)3 . 18H2 O + NaF + 9Na2CO3 → [5Al(OH)3.Al(OH)2F] +

9Na2SO4+NaHCO3 + 8 CO2 + 45 H2O

3 Al2 (SO4)3 . 18H2 O + NaF +17NaHCO3 → [5Al(OH)3.Al(OH)2F] + 9Na2SO4+ 17

CO2 + 18 H2O

Raw estimation of required dosage:

A preliminary estimate is made on the amounts of alum needed using the reundlich based
formula developed by Dahi et al. 1995:
A= (Fr - Ft) · V/(a · Ft 1/b)

Where:
A is the amount of alum required, g.
Fr is the fluoride concentration in the raw water, mg/l.
Ft is the residual fluoride concentration in the treated water, mg/l.
V is the volume of water to be treated in batch, l.
a is the sorption capacity constant, l (1-1/b) mg 2/bg-1
b is the sorption intensity constant,
The results have shown that, for pH = 6.7 and required residual fluoride between 1 and
1.5 mg/l, a = 6 and b= 1.33. The amount of lime required is far more difficult to estimate
theoretically as it depends on the quality of lime, the alkalinity and pH of the raw water
and the fluoride removal itself. Our experience have however shown that lime addition
may be 20-50 per cent of the alum dosage

Salient features of Nalgonda technique

‧ No regeneration of media
‧ No handling of caustic acids and alkalies
‧ Readily available chemicals used in conventional municipal water treatment are only
required
‧ Adaptable to domestic use.

Flexible upto several thousands m3 Discarding the sludge from the Nalgonda process
is a serious environmental health problem. The sludge is toxic as it contains the removed
fluoride in a concentrated form. In nature the fluoride would be expected to mobilize
rapidly due to weathering processes. The free fluoride ion would then be subject to
infiltration to underground or rain run off. Another major cause for concern with the
Nalagonda technique is that if the dose of alum is not adhered to, there is a possibility of
excess aluminum contaminating the water6. The maximum contamination of aluminum
permitted is 0.03 mg to 0.2 mg/litre of water according to the Indian Standards4, as
excess aluminum is suspected to cause Alzheimer’s disease.

Activated Carbons

Activated Carbons prepared from paddy husk has a high defluoridation capacity.
Similarly activated carbon prepared from cotton waste, coffee waste and coconut waste
were tried for defluoridation but all these materials are academic interest only.

Activated charcoals which are effective for fluoride removal, when impregnated with
metal ions have an increase in their fluoride adsorption capacity by 3 to 5 times that of
plain activated charcoal. The defluoridating ability of an activated charcoal impregnated
with different types of metal ions, depends on two factors:

The degree of adsorption of the metal ion on the activated charcoal and
The fluoride ion affinity of the metal ion.

A comparative study done by impregnation of metal ions such as ZrOCl2, CaO, Alum,
CaCl2 and Borax in activated charcoal gives following results.

Volume(L)ZrOCl2CaOAlumCaCl2Na2B4O7Unimpregnated
charcoal.
6.5 mg/L test solution2.52 mg/L
Tapwater
10.140.121.061.875.645.486.04
21.11.321.484.735.985.696.08
32.461.903.055.596.015.736.14
43.572.334.55.986.075.866.20

Table: Residual fluoride in mg/L after adsorption from stanard fluoride solution (6.5
mg/L) by different metal ion impregnated activated charcoals in successive litre lots

The activated charcoal when impregnated with ZnOCl2 proved to be an effective

defluoridating agent for treating effluents of lower fluoride concentrations from 10-2
mg/L. Zirconium is generally non-toxic as and element or in compounds and the oral
toxicity is low: OSHA standards for pulmonary exposure specify a threshold limit value
of 5mg Zirconium per m3 and 10 mg aluminium per m3, respectively.

Based on Ion exchange:

Anion exchangers:

These are found to remove fluorides either by hydroxyl cycle or chloride cycle along with
other anions. Polystyrene anion exchange resin and basic quaternary ammonium type are
used to remove fluoride along with other anions. Poly anion exchange resin, Tulsion A -
27, Deacodite FF (IP), Lawatit MIH - 59, Amberlite IRA 400 are the few example.
Cation exchange resin :

Cation exchange resins impregnable with alum solution have been found to act as
defluoridating agents. “Avaram bark” based cation exchange resin works effectively in
removing fluoride from water. Bhakuni 7 compared the performance of defluoron - 1 and
2, Carnion, Wasoresin -14 and polystyrene cation exchange resin.

Conclusion:

Fluoride is most dangerous pollutent in ground water. Fluoride in drinking water is

1.5ppm as per WHO standards. As per survey conducted under water technology mission
25 million people residing in 8,700 villages of India are effected by fluorosis. Health
effects caused by fluoride are incurable. Excess fluoride may be present in ground water
in some locations due to the leaching of fluoride rich minerals, which is dependent on
hydrogeological conditions. There are many defluoridation methods reported in literature.
These include use of alum and lime, bone ash, activated alumina etc. A review of the
results obtained by absorption of fluoride by several metal ions impregnated char coal
was done and

Zirconium ion showed greater efficiency. Effects of contact time, pH, alum dosage etc on
defluoridation are presented. Past experience has clearly underscored the need for
addressing issues such as long term sustainability of the system in terms of reliability of
source yield, the infrastructural facilities that could be mobilized at local level for O &
M, the financial capability of the agencies vested with the O & M responsibility as also
policy guidelines with respect to funding of the systems, government agencies have
recognized fluorosis as a serious concern and suggested that the water used for drinking
must be treated for removal of excess fluorides. Therefore, there should be a concerted
effort by the government, NGOs, Universities and public to tackle the problem.

Bibilography:

1. Indian journal of Chemical Technology “study on defluoridation of drinking water by

impregnation of metal ions” vol 13,july.2006.
2. Defluoridation processes G.Karthikeyan and A. Shunmuga sundarraj, internet.
3. Flouride in water; an overview UNICEF.
4. Water quality in sustainable water management: Sudhakar M rao, P mamata, IISc.
5. www.nri.org/whirl.
6. Water Quality fact survey, British geological
Document By
SANTOSH BHARADWAJ REDDY
Email: [email protected]
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