DEFLUORIDATION

IMPORTANCE AND TECHNIQUES

PRESENTED BY: SANKET AGRAWAL M.TECH 1ST YEAR, ENVIRONMENT ENGG. ADVANCED WATER AND WASTEWATER TREATMENT

DEFLUORIDATION: IMPORTANCE

Though water is regarded as a human right rather than a human need, the access to closer and cleaner drinking water is still a distant dream for about one-sixth of humanity on this planet.

CHEMICAL PROFILE
One Electron short to Inert gas configuration. Most Electronegative and Reactive of all elements. Pale Yellow-Green Irritating gas. 0.3g/kg of Earths crust.

GEOCHEMISTRY
The alkaline water can mobilize F from soil , weathered rocks and CaF2.
CaF2 + 2HCO3 CaCO3 + 2F + H2O + CO2
RAIN WATER
CO2 FROM SOIL & AIR
LEACH SALTS (NaCl, NaHCO3)

CaF2 has solubility product of

Ksp= [F]2[Ca2+] = 4.0 1011

Waters with low content of calcium should have high fluoride concentration.

FLOURIDE-BEARING COMPOUNDS via FERTILIZERS

SOURCES OF FLUORIDE
NATURAL
CHIEF SOURCE: PARENT ROCK
(GRANITE ROCK 20-3600ppm)

OTHER
INDUSTRIES POWER PLANTS

SOIL
200-300ppm

FOOD
HIGH IN TEA PLANTS 1000 TIMES THAT OF SOIL

WATER
HIGHEST: 2800ppm SURFACE: 0.1-0.3

CIGARATTES: 236ppm TEFLON-LINED COOKWARES: 3ppm

FERTILISERS

SEA WATER: 1.2-1.5

Average dietary intake of fluoride for adults living in area with 1.0ppm fluoride in water is b/w 0.02-0.048mg/kg/day. The presence of diet rich in calcium reduces the fluoride absorption in human.

GLOBAL SCENARIO
Affected (poisoned) more than 25 nations across the world. More than 200 million people across the globe are at risk of fluorosis. China more than 1/10th of population affected by fluorosis. In Mexico, 5 million people(6% population) affected. In Ethiopian Rift Valley fluoride conc. in range of 1.5 to 177 ppm encountered. Tanzania (8-12.7ppm) most severely affected country. (Acc. to WHO (1-1.5ppm)standards nearly 30% water sources are unfit.)

INDIAN SCENARIO
20 States affected. Affecting more than 66 million people including 6 million children under 14 years age. One of the most alarming public health problem of the country. Rajasthan, Andhra Pradesh and Assam are most endemic. People of Rajasthan and Assam are forced to consume water with fluoride concentration up to 44ppm and 23ppm, resp.

Delhi has natural maximum fluoride concentration of 32ppm.

EFFECTS OF FLUORIDE
EFFECTS

Dental Effects

Skeletal

Effects

Other Adverse Effects

DENTAL CARIES

SKELETAL FLUOROSIS

CARCINOGENICITY

DENTAL FLUOROSIS

GASTROINTESTINAL EFFECTS

Fluoride has both beneficial and detrimental effects on human health with only a narrow range between intakes that are associated with these effects.

DENTAL CARIES(Tooth Decay)

Dental caries is an infectious and multifactorial disease causing demineralization of inorganic components of teeth. Untreated caries can lead to:

Incapacitating pain Bacterial infection Tooth extraction Loss of dental function.

Fluoride aids the calcium and phosphate ions chemical reaction producing a crystal surface much less soluble in acid enhancing remineralization.
WHO permissible limits for preventing Dental Caries is 0.5-1.2ppm.
CDC hails water fluoridation as one of the ten most important public health measures currently available. Globally, the population consuming fluoridated drinking water were estimated as about 355 million in 2005.

DENTAL FLUOROSIS
Irreversible toxic effect on the tooth forming cells It ranges from barely visible white striations on the teeth through to gross defects and staining of the enamel.
MECHANISM

The calcium rich constituents of teeth, viz. enamel and dentin, have strong affinity for fluoride during the formation of teeth. Fluoride combines with calcium forming calcium fluoroapatite crystals during mineralization. So, as fluoride accumulates, calcium is lost from the teeth. Due to loss of calcium, enamel becomes more porous, discolored and prone to wear.
EFFECTS

unfavorable effects on individuals personality. It is hard to smile for a person with dental fluorosis. Inferiority complex, likely to experience embarrassment, isolation and discrimination. Can lead to deep psychological depression.

SKELETAL FLUOROSIS
Fluoride replaces the hydroxyl ion from hydroxyapatite, a mineral phase during formation of bone forming hydroxyfluorapatite, altering the mineral structure of bones this leads to the formation of denser bones which are more fragile and brittle.
Occurrence of fluorosis depends upon many factors like nutritional status and diet, climate, amount of exposure, source of fluoride intake, etc. (observed even in range of 0.4-1.4ppm)

Physical Effects: kyphosis, scoliosis, paralysis, deafness, Genu vaum (bow legs), etc. Social Effects: loss of work & livelihoods, psychological trauma, impaired marriage possibilities for girls, inability to meet high medical costs and above all, the loss of will to live.

DEFLUORIDATION TECHNIQUES

The lack of excess to clean water denies the most essential of all rights, the right to life

DEFLUORIDATION TECHNIQUES
CLASSIFICATION

COAGULATION TECHNIQUES

ADSORPTION/ ION EXCHANGE

ELECTROCHEMICAL METHODS

MEMBRANE METHODS

PRECIPITATION
(LIME , CaSO4)

BY BONE, BONE CHAR,CLAYS

ELECROCOAGULATION

REVERSE OSMOSIS

COPRECIPITATION

(BY ALUM & LIME)

ACTIVATED ALUMINA

ELECTROSORPTION

NANO FILTRATION

ELECTRODIALYSIS

NALGONDA TECHNIQUE (Alum-lime Co-precipitation)

It involves addition of alum, lime, and bleaching powder to raw water.
Sodium aluminates or lime hastens the settlement of precipitate and bleaching powder insures disinfection.

Fluoride get adsorbed on sticky gelatinous Al(OH)3 flocs during sweep coagulation. Al+3 +H2O Polynuclear-Hydroxo Complexes + H+
H+ ions will neutralize the alkalinity. If initial alkalinity is low there will be further reduction buffering capacity destroyed pH drop rapidly.

But alkalinity is must for hydroxide floc formation.

Fig. Domestic Treatment Precipitation Settling Filtration

Hence artificial alkalinity in the form of lime or soda ash is added with the alum.

ADVANTAGES
The absence of regeneration of media Use of readily available chemicals. Easy operation and maintenance. Low cost chemicals used. Simultaneous removal of color, odor, turbidity, bacteria, and organic contaminants.

DISADVANTAGES
Did not achieve a great degree of success in field applications both as hand-pump-based units and as smaller domestic units. Medium efficiency (70%). Large dose requirement of aluminum sulfate (7001200 mg/L). Difficulty in controlling alum and lime dosages for different sources. High hardness of the treated water. Increased pH.

ELECTRODIALYSIS
The removal of ionic components from aqueous solution through ion exchange membranes is carried out under the driving force of an electrical field.

CONCENTRATE

CONCENTRATE

C(-)

A(+)

A(+)

SELECTION OF ELECTRODIALYSIS MEMBRANE

Permselectivity, A low water transport number, Reasonably good electrical conductivity, Good chemical resistance especially to oxidation, Adequate mechanical strength, Dimensional stability.

MEMBRANES USED
Perfluorosulfonic acid polymer: Nonporous ,Isotropic, 50500 Poly(styrene-co-divinylbenzene ): Nonporous, Isotropic, 100500 ACS-CMX membranes: Monovalent Anion Permselective

EFFICIENCY
Current efficiency is a measure of how effective ions are transported across the ion exchange membranes for a given applied current.

5000 mg/L TDS and fluoride up to 15 mg/L can be reduced to 600 mg/L TDS and <1.5 mg/L fluoride.

ADVANTAGES
Simultaneous defluoridation and desalination of brackish water. Commercially established. More economical than pressure driven processes. More resistant to fouling ( Electrodialysis Reversal Systems). High capacity. Less space requirement.

LIMITATIONS
Require high degree of pretreatment. Ineffective in removing low-molecular-mass non-charged compounds. Not suitable for waters of low salinity (conductivity < 0.5 Ms). Disposal of concentrate: (Dilution in saline water, deep well storage, combustion, industrial reuse, etc.)

REFERENCES
Ayoob, S. & Gupta, A.K. (2006) Fluoride in Drinking Water: A Review on the Status and Stress Effects. Critical Rev. Environ. Sci. Technol.
Ayoob, S., Gupta, A.K. & Venugopal, T.B. (2008) A conceptual overview on sustainable technologies for defluoridation of drinking water, Critical Rev. Environ. Sci. Technol.

Frederick B. &Daniel E.(2009) Defining the concentrate disposal problem and identifying potential solutions. Critical Rev. Environ. Sci. Technol. Turnbull S., Benning F., G. W. Feldmann, Linch L., Mc Harness, & Richards S. Analysis and disposal of fluorine. Industrial and engineering chemistry. Vol.39, No.3.
Adhikary, S.K., Tipnis, U.K., Harkare, W.P., and Govindan, K.P. 1989. Defluoridation During Desalination of Brackish Water by Electrodialysis. Desalination,71, 301312 Electrodialysis Source: http://en.wikipedia.org/w/index.php? oldid=498361104.

Thank You