Flouride in Ground Water

Fluoride in groundwater:
Overview and evaluation of removal

methods
L. Feenstra
L. Vasak
J. Griffioen
Utrecht
September 2007
Report nr. SP 2007-1

International Groundwater Resources Assessment Centre Report nr. SP 2007-1
Table of contents
Summary.............................................................................................................................. ii
1 Introduction .....................................................................................................................1
1.1 Special projects of IGRAC.................................................................................................................. 1
1.2 Occurrence of fluoride ........................................................................................................................ 1
1.3 Outline of the report............................................................................................................................ 1
2 Overview of removal methods .........................................................................................2

2.1 Common methods............................................................................................................................... 2
2.2 New technologies ............................................................................................................................... 4
3 Setup, scale of use and location .......................................................................................7
4 Evaluation ........................................................................................................................8
5 Selection............................................................................................................................9
References ...........................................................................................................................11
Appendix 1: Fact sheets fluoride removal technologies ....................................................13
Figures
Figure 1: Decision tree for fluoride removal techniques applicable in industrialized countries.........9
Figure 2: Decision tree for fluoride removal techniques applicable in developing countries. .........10
Tables
Table 1: Fluoride removal methods (based on Heidweiller, 1990; Pickard and Bari, 2004 and BGS,
2003) ..............................................................................................................................3
Table 2: Differences in characterization of water treatment methods in conventional systems in
industrialized and developing countries (Fawell et al., 2006) ...........................................7
Table 3: General comparison of the most promising defluoridation methods used in developing
countries (Fawell et al., 2006)..........................................................................................8
i
Summary
In this report information is given about methods for the removal of fluoride from groundwater. The
methods can be used by domestic well owners and communal water suppliers. Based on available
information, a matrix is composed to give an idea about the applicability of the methods for some
given situations.
Fluoride removal methods

Methods domestic community domestic community domestic community
+ + + + + +
brackish brackish
low costs low costs high F removal high F removal water water
Activated Alumina
Ion exchange
Reverse osmosis
Electrodialysis
Nalgonda process
Contact precipitation
Bone Charcoal
Calcined Clay
Water Pyramid/Solar Dew
The colours in the matrix correspond with the appropriateness of the method for the given situation:
• Green colour means that the method is very suitable
• Orange colour means average suitability
• Red colour means that the method is unattractive or not applicable for the given situation.
The Nalgonda process, Bone charcoal and Calcined clay are low costs methods for domestic use. On a
community scale, the Nalgonda process is also a low cost option. If a high fluoride removal is
necessary then activated alumina, reverse osmosis and electrodialysis are preferred methods.
For brackish water only reverse osmosis, electrodialysis and the Water Pyramid/Solar Dew method
can be used.
ii
1 Introduction
1.1 Special projects of IGRAC

The International Groundwater Resources Assessment Centre (IGRAC) aims to facilitate and promote
world-wide exchange of groundwater knowledge. IGRAC focuses on activities that are prompted by
the international groundwater community.
IGRAC’s special projects intend to collect, analyse and display information on specific groundwater
issues relevant to development of groundwater resources on various scales. Occurrence of hazardous
compounds in groundwater is one of these issues. In 2004, IGRAC reviewed available information
about groundwater contaminated with fluoride and displayed the probability occurrence of fluoride on
continental maps (Brunt et al, 2004).
In this report, an overview is given of fluoride removal methods.
1.2 Occurrence of fluoride

Fluoride is an ion of the chemical element fluorine which belongs to the halogen group. Fluoride has a
significant mitigating effect against dental caries if the concentration is approximately 1 mg/l.
However, continuing consumption of higher concentrations can cause dental fluorosis and in extreme
cases even skeletal fluorosis. The WHO guideline value for fluoride in drinking water is 1,5 mg/l
(WMO, 2004). High fluoride concentrations are especially critical in developing countries, largely
because of lack of suitable infrastructure for treatment.
In groundwater, the natural concentration of fluoride depends on the geological, chemical and physical
characteristics of the aquifer, the porosity and acidity of the soil and rocks, the temperature, the action
of other chemical elements, and the depth of the aquifer.
Because of the large number of variables, the fluoride concentrations in groundwater (e.g. in Kenya,
South Africa and India) can range from well under 1 mg/l to more than 35 mg/l.
1.3 Outline of the report

In chapter 2 an overview is given of removal methods. The methods are briefly described using fact
sheets. Also some new interesting technologies are mentioned. The methods are intercompared in a
table according to relevant criteria such as removal efficiency, capacity, costs, required skill and
advantages and disadvantages.
Chapter 3 deals with the set-up of a fluoride removal system, the scale of use and the location for
application (developing country or industrialized regions).
An evaluation of the methods is given in chapter 4.
Chapter 5 deals with the selection process. To help water users by choosing the most appropriate
methods for their situation, process selection decision trees were made for both industrialized regions
and developing countries.
The electronic version of this report is available on the IGRAC web-site: www.igrac.nl
1
2 Overview of removal methods
2.1 Common methods

The common methods used for the removal of fluoride from drinking water are divided in the
following four categories:
• precipitation;
• adsorption and ion-exchange;
• membrane filtration processes;
• distillation.
Precipitation
Precipitation processes involve addition of chemicals and formation of fluoride precipitates. Among
these are precipitations with calcium and aluminium salts. Precipitation chemicals must be added daily
in batches and precipitation techniques produce a certain amount of sludge every day.
Adsorption and ion-exchange

Adsorption processes involve the passage of water through a contact bed where fluoride is removed by
ion exchange or surface chemical reaction with the solid bed matrix. After a period of operation, a
saturated column must be refilled or regenerated. The different adsorbents used for fluoride removal
include activated alumina, carbon, bone charcoal and synthetic ion exchange resins.
Membrane filtration process

Reverse osmosis and electrodialysis are two membrane filtration processes which can be used for
removal of fluoride.
Distillation
Distillation units can also be used for treating the drinking water. Large scale electrodialysis plants are
already used for making drinking water out of brackish water with high fluoride concentrations (Zakia
et al., 2001; Werner and von Gottberg, 1998). In many parts of North Africa, water is brackish and
contains over 1.5 mg/l fluoride.
In appendix 1, eight fact sheets are presented for the most common fluoride removal technologies.
Information is given about the following aspects:
• process and technology used
• equipment required
• removal performance
• scale/flow rate
• experience/state of the art
• costs
• advantages and disadvantages
• contact details and additional information.
Reverse osmosis, electro dialysis and distillation are advanced, large scale treatment technologies
which are difficult to use in less advanced regions. However reverse osmosis units are nowadays also
deliverable for household scale. Small scale point-of-use techniques like Nalgonda technique, Bone
Charcoal, Contact Precipitation and Clay are more suitable for developing countries. Activated
alumina and reverse osmosis are the most common technologies. Activated alumina can concurrently
remove other anions, such as arsenate. Reverse osmosis achieves significant removal of virtually all
dissolved contaminants. An overview of the fluoride removal methods is given in table 1.
2
Table 1: Fluoride removal methods (based on Heidweiller, 1990; Pickard and Bari, 2004 and BGS, 2003)
Techniques Household Community Removal WHO-level Water Loss Capacity/dose Working PH Interferences Operator skill Relative costs Advantages Disadvantages
level efficiency (%) feasible
Precipitation
Alum (aluminumsulphate) x x >90% yes 1-2% 150 mg/mg F non-specific - low medium-high established process sludge produced
treated water is acidic
residual Al present
Lime x x >90% yes 1-2% 30 mg/mg F non-specific - low medium-high established process sludge produced
treated water is alkaline
Alum + Lime (Nalgonda) x x 70-90% possible 1-2% 150 mg alum + 7 mg lime/mg F non-specific - low medium-high low-tech sludge produced
optimum pH 6.5 established process high chemical dose
residual Al present
Gypsum + fluorite x x ? no 1-2% 5 mg gypsum + <2 mg fluorite/mg F non-specific - medium low-medium simple requires trained operators
low efficiency, high residual CaSO4
Calcium choride x x > 90% possible 1-2% 3 mg CaCl2/mg F 6.5-8
Adsorption/ion exchange
activated carbon x x >90% yes 1-2% variable <3 many medium high - many interferences
large pH changes before and after treatment
plant carbon x x >90% ? 1-2% 300 mg F/kg 7- medium low-medium locally deleverable requires soaking in potassium
hydroxide
zeolites x x? >90% yes 1-2% 100 mg F/kg non-specific - medium high - poor capacity
defluoron 2 x x >90% 1-2% 360 g F/m3 non-specific alkalinity medium medium - disposal of chemicals used in resin
regeneration
clay pots x 60-70% possible 1-2% 80 mg F/kg non-specific - low low locally deleverable low capacity, slow
activated alumina x x 85-95% yes 1-2% 100 mg alumina/mg F (1200 g F/m3) 5.5 alkalinity low medium proven effectiveness source water pH adjustment to 6.5
will treat current F and As spent regeneration solution contains
low energy consumption high F (and As) concentrations
chemical and sludge handling needed
sludge typically non-hazardous efficiency dependent on source water
bone x x low? possible 1-2% 900 g F/m3 >7 arsenic low low locally available may give taste; degenerates
not universally accepted
bone char x x possible 1-2% 1000 g F/m3 >7 arsenic low low locally available not universally accepted
high capacity
Other
electrodialysis x 85-95% yes 20-30% high non-specific turbidity medium very high will treat current F and As high water loss
and other contaminants high energy consumption
possitive public perception high (capital) costs
reverse osmosis x 85-95 yes 40-60% high non-specific turbidity medium very high will treat current F and As high water loss
and other contaminants high energy consumption
possitive public perception high (capital) costs
3
From table 1 it can be seen that majority of low -costtechnology methods rely on precipitation or
flocculation or adsorption/ion-exchange processes. The Nalgonda 1 technique is probably the best
known and most established method. This method uses a combination of aluminium sulphate and
lime. The method can be used at a domestic scale (in buckets) or community scale. It has moderate
costs and required materials are easily available. The removal efficiency is however moderate.
Activated alumina and bone material are among the most appropriate removal methods (appropriate
technology = most effective method). Activated alumina method also removes arsenic, but may not
always be available or affordable. Bone products are not readily acceptable in some areas. Other
highly efficient methods of removal include electro dialysis and reverse osmosis, but these methods
tend to involve higher technology and higher costs and are therefore less suitable for many
applications in developing countries.
2.2 New technologies

Besides the methods mentioned in table 1 several new methods have been introduced in recent years.
These new technologies include:
• Crystalactor®
• Memstill® technology
• The WaterPyramid® solution
• The Solar Dew Collector system
• Boiling with brushite and calcite
• Use of new absorbents
Crystalactor®
In the Netherlands a new type of contact precipitator, named the Crystalactor®, is developed by DHV
(Giesen, 1998). The Crystalactor® is a fluidized-bed type crystallizer also called a pellet reactor.
In the reactor fluoride is removed from the water while calcium

fluoride pellets with a diameter of 1 mm are produced. The major
advantages of the Crytalactor® are that (1) the installation is
compact, (2) calcium fluoride pellets with a high-purity are
produced, (3) the produced pelltes have an extremely low water
content 95% tot 10% moisture) and (4) the pellets can be reused.
Costs comparisons show that the total treatment costs are typically
approximately 25% of the costs for conventional precipitation.
However the Crystalactor® is more suitable for wastewaters with
high fluoride concentrations (> 10 mg/l). For treating drinking
water, the Crystalactor® is only advisable in case of high fluoride
concentrations (> 10 or 20 mg/l). For reaching a concentration
below 1 mg/l fluoride, a second technique must be used afterwards
(for example I.E).
Source: DHV
1
The Nalgonda technique is named after the Nalgonda District in India where it was first developed.
4
Memstill® technology
The Netherlands Organisation of Applied Scientific Research (TNO) has developed a membrane-
based distillation concept which radically improves the economy and ecology of existing desalination
technology for seawater and brackish water. This so-called "Memstill® technology" combines multi-
stage flash and multi-effect distillation modes into one membrane module (Hanemaaijer et al., 2007).
Cold feed water takes up heat in the condenser channel

through condensation of water vapour, after which a small
amount of (waste) heat is added, and flows counter
currently back via the membrane channel. Driven by the
small added heat, water evaporates through the membrane,
and is discharged as cold condensate. The cooled brine is
disposed, or extra concentrated in a next module.
The Memstill® technology can produce (drinking)water at

a cost well below that of existing technologies like reverse
osmosis and distillation.
With the Memstill® technology also anions like fluoride
and arsenic are removed. It is expected that the Memstill®
technology will be also developed for small scale
applications using solar heat.
Source: TNO
The WaterPyramid® solution

http://www.aaws.nl/home.htm - #http://www.aaws.nl/home.htm - #Aqua-Aero WaterSystems has
developed the WaterPyramid® concept for tropical, rural areas (Aqua-Aero, 2007).
http://www.aaws.nl/home.htm - #http://www.aaws.nl/home.htm - #http://www.aaws.nl/home.htm -
#The WaterPyramid® makes use of simple technology to process clean drinking water out of salt,
brackish or polluted water. One of the pollutants could be fluoride. Most of the energy needed to clean
the water is obtained from the sun.
WaterPyramid® with a total area of 600 m2 and situated under favourable tropical conditions, can
produce up to 1250 litres of fresh water a day. The production rate is dependant on site specific factors
such as climate and temperature, cloudiness and wind activity. Desalination is driven by the sun and
the energy needed for pressuring the WaterPyramid® is obtained using solar cells in combination with
a battery back-up system. Intermittent peak demands in electricity, related to e.g. (borehole) pumping
and maintenance, are covered using a small generator system.
5
Source: Aqua-Aero WaterSystems
The Solar Dew Collector system

Solar Dew (Solar Dew, 2007) developed a new porous membrane to purify water using solar energy.
The technique is similar to the WaterPyramid®.
Water sweats through the membrane, evaporates on the membrane’s surface and increases the air
humidity in the evaporation chamber.
Based on a temperature difference, pure water condenses on the cooler surfaces of the system.
Source: Solar Dew
The product water quality is very constant and similar to that of distilled water. The quantity depends
on the intensity of the solar radiation. To avoid crystallization, the brine has to be drained periodically.
The system is able to process: sea-, brackish or contaminated waste water (e.g. with heavy metals, oil
residue, boron, fluoride) with an allowable pH range of 5-11.
Boiling with Brushite and Calcite

Existing methods for defluoridating drinking water involve expensive high technology or are slow,
inefficient and/or unhygienic. In Larsen and Pearce (2002), a new method is suggested, using a
suspension of the minerals brushite (CaHPO4.2H2O) and calcite (calciumcarbonaat) followed by
boiling. On a laboratory scale, this method gave good results. It was concluded that boiling a
brushite/calcite suspension rapidly converts the two salts to apatite which incorporates fluoride if
present in solution. This process may be exploited to defluoridate drinking water.
New adsorbents for adsorption of fluoride

In recent years, several new adsorbents for adsorption of fluoride have been investigated. For example,
lanthanum-impregnated silica-gel, La(II) and Y(III)-impregnated alumina and aluminium-impregnated
carbon have been used for adsorption of fluoride successfully by Raichur and Jyoti Basu (2001). The
use of waste materials and low-cost materials as adsorbents for fluoride has been examined. Raichur
and Jyoti Basu (2001) paid also attention to adsorption of fluoride onto mixed rare earth oxides. The
rare earth oxides are naturally occurring in Southern India. The method is simple and has shown great
potential for selective removal of fluoride. It was found that the mixture of rare earth elements adsorb
fluoride rapidly and effectively. Most of the adsorption took place in the first 5-10 min. The adsorbent
was found to load as high as 12.5 mg of fluoride per gram of adsorbent. The optimum pH was found to
be about 6.5 for fluoride adsorption which makes it very suitable for use in drinking water treatment.
Other ions such as sulphate and nitrate (up to 100 mg/l) did not greatly affect the adsorption of
fluoride thereby indicating that the rare earth oxide is a selective adsorbent for fluoride.
6
3 Setup, scale of use and location
Defluoridation of drinking-water is technically feasible at point-of-use (at the tap), for small
communities of users (e.g. wellhead application) and for large drinking-water supplies. Point-of-use
systems can produce sufficient quantities of treated water for drinking and cooking requirements of
several persons. Numerous plumbed-in, small distillation units are marketed that have been tested and
can produce 10 litres per day or much larger volumes. Many certified low pressure reverse osmosis
units are available with rated capacities in the range of 30-100 litres per day. Point-of-use
defluoridation using activated alumina anion exchange is capable of removing fluoride from small
volumes of water, but international performance standards have not been developed to date.
Community-sized, commercially available, package water treatment systems that use activated
alumina or reverse osmosis technology also exist. They can be purchased as a complete unit that can
be readily shipped and installed on-site.
These can produce hundreds of litres or more of treated, low fluoride water per day. Large
defluoridation systems can also be designed and constructed on-site to engineer’s specifications.
Conventional water treatment, as carried out in both rural and urban areas in industrialized countries,
takes place typically:
• in a water works without direct involvement of the users,
• under the supervision of skilled operators, and
• where the affordability of treatment is taken for granted.
In such cases the method of treatment is well established and well controlled. However, it requires
major input of resources and may have serious limitations or disadvantages in less-developed
countries, especially in rural areas where the water users are scattered or the supply is entirely local.
Here treatment may only be feasible at a decentralized level, e.g. at community village level or at
household level (see table 2).
Table 2: Differences in characterization of water treatment methods in conventional systems in

industrialized and developing countries (Fawell et al., 2006)
Criteria Industrialized Countries Developing countries
Set-up and water Always continuous, often in columns Often discontinuous in columns
flow Fill and draw in batch
Scale and treatment Always at water works, usually close to At water works
site water source At village community level
At household level
Treatment Contact precipitation Bone charcoal
media/process Activated alumina Contact precipitation
Synthetic resins Nalgonda
Reverse osmosis Activated alumina
Electrodialysis Clay
Other naturally occurring media
7
4 Evaluation
There is not a universal method which is appropriate under all social, financial, economic,
environmental and technical conditions. None of the methods has been implemented successfully at a
large scale in many parts of the world. All available defluoridation methods do have disadvantages,
such as:
1. High Cost-Tech; i.e. either the price and/or the technology is high, demanding imported spare parts,
continuous power supply, expensive chemicals, skilled operation or regeneration, etc. Reverse
osmosis, ion exchange and activated alumina may thus be categorized as high cost-tech methods.
2. Limited efficiency; i.e. the method does not permit sufficient removal of the fluoride, even when
appropriate dosage is used. As in the Nalgonda technique, the residual concentration would often be
higher than 1 mg/l, unless the raw water concentration itself is relatively low.
3. Unobserved breakthrough; i.e. the fluoride concentration in the treated water may rise gradually or
suddenly, typically when a medium in a treatment column is exhausted or even when the flow is out of
control. As in the case of bone charcoal and other column filters, these techniques necessitate frequent
monitoring of fluoride residual, or at least the rate and the volume of treated water, if unobserved
breakthrough or the loss of removal capacity is to be avoided.
4. Limited capacity; while the removal capacity of bone charcoal or activated alumina may be about 2
mg of fluoride per gram of medium, much higher amounts of calcined clay for example have to be
used in order to obtain appropriate removal.
5. Deteriorated water quality; this would by nature result in excessively high pH values, normally
above 10. The water quality may also deteriorate due to bacterial grow, poorly prepared medium (bone
charcoal) or due to medium escaping from the treatment container, e.g. ion exchange, alumina,
Nalgonda sludge, etc.
6. Taboo limitations; in particular, the bone charcoal method is culturally not acceptable to Hindus.
Bone charcoal originating from pigs may be questioned by Muslims. The charring of bones has also
been reported to be unacceptable to villagers in North Thailand.
General comparison of the methods is given in table 3.

Table 3: General comparison of the most promising defluoridation methods used in developing countries
(Fawell et al., 2006).
Advantages Defluoridation methods
BC CP Nal AA Cl
No daily dosage of chemicals, i.e. no daily working load + - - + +
Dosage designed for actual F conc. Independent of unit or plant - + + - -
No risk of false treatment due to break point - + + - -
Removal capacity of medium is independent of F concentration - + - - -
No regeneration or renewal of medium is required - + + - -
High removal efficiency can be ensured + + - + -
Easy to construct, even by the users + + ++ + +
Construction materials are cheap and widely available + + ++ + +
Can be sized for one or several families or a group, e.g. a school + ++ + + -
No risk of medium/chemicals unacceptability - -/+ + + -
No risk of deterioration of the original water quality -/+ + -/+ -/+ -
BC = bone charcoal; CP = contact precipitation; Nal = Nalgonda technique of aluminium + = advantage
sulfate and lime; AA = activated alumina; Cl = calcined clay; “risk” means in some cases - = disadvantage
8
5 Selection
For the selection of an appropriate fluoride removal method in industrial and developing countries two
process selection decision trees have been made.
A decision tree for the industrialized countries is shown in figure 1.

Error! Objects cannot be created from editing field codes.
Figure 1: Decision tree for fluoride removal techniques applicable in industrialized countries
Activated Alumina and RO/ED are the favourite techniques for industrial countries when high
capacity and proven technology is needed.
For small applications contact precipitation or ion exchange (in case the water contains only high
concentrations of fluoride) is recommended.
A decision tree for the developing countries is shown in figure 2.
9
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High F +
X BC Scale up to y y
CP much other CP
CP community
IE anions
IE level needed
n n
CP
BC IE
IE
y Frequent
BC monitoring
possible
CP
IE
Figure 2: Decision tree for fluoride removal techniques applicable in developing countries.
Activated alumina is the favourable technique for developing countries in case high removal
efficiency and high capacity is needed.
For situations where moderate removal efficiency is sufficient, the Nalgonda technique is preferable.
In other situations (high removal efficiency, small scale) contact precipitation or ion exchange (only
high F-ions) is advisable. Bone charcoal can also be used if frequent monitoring is possible.
10
References
Aqua-Aero WaterSystems, 2007.
WaterPyramid. http://www.waterpyramid.nl
British Geological Survey (BGS), 2003.

Water Quality Fact Sheet: Fluoride. WaterAid International site.
http://www.wateraid.org/documents/plugin_documents/fluoride1.pdf.pdf
Brunt, R., Vasak, L. and Griffioen, J., 2004.

Fluoride in groundwater: Probability of occurrence of excessive concentration on global scale. Report
SP 2004-2, International Groundwater Resources Assessment Centre (IGRAC).
Fawell, J., Bailey, K., Chilton, J., Dahi, E., Fewtrell, L. and Magara, Y., 2006.
Fluoride in Drinking water, World Health Organisation, IWA Publishing, Alliance House, 12 Caxton
Street, London SW1H 0QS, UK.
Giesen, A., 1998.

Fluoride removal at low costs. European Semiconductor 20 (1998), 4. pp 103-105.
Heidweiller, V.M.L., 1992.

Fluoride Removal Methods. In Endemic fluorosis in developing countries: causes, effects and possible
solutions (Frencken, J.E., editor). Publication number 91.082, NIPG-TNO, Leiden, The Netherlands,
1992
Larsen, M.J. and Pearce, E.I.F., 2002.

Defluoridation of Drinking Water by Boiling with Brushite and Calcite. Caries Research
2002;36:341-346 (DOI: 10.1159/000065964). Department of Dental Pathology, Endodontology
and Operative Dentistry Royal Dental College, Aarhus.
Pickard, B. and Bari, M., 2004.

Feasibility of Water Treatment Technologies for Arsenic and Fluoride removal from groundwater.
AWWA Water Quality Technology Conference, San Antonio, Texas; November 2004.
https://chppm-
www.apgea.army.mil/dehe/pgm31/newpubs/WQTC2004ArsenicProc(Pickard%20and%20Bari).pdf
Raichur, A.M. and Basu Jyoti M., 2001.

Adsorption of fluoride onto mixed rare earth oxides. Separation and Purification Technology 24(1-
2):pp. 121-127.
Solar Dew, 2007.

The Solar Dew Collector Sytem. http://www.solardew.com/index2.html
Hanemaaijer, J.H., van Medevoort, J., Jansen, A., van Sonsbeek, E., Hylkema, H., Biemans, R.,
Nelemans, B.and Stikker, A., 2007.
Memstill Membrane Distillation: A near future technology for sea water desalination,
Paper presented at the International Desalination Conference, June 2007, Aruba.
Werner, T.E. and von Gottberg, A.J.M., 1998.

Five Billion Gallons later- Operating Experience at City of Suffolk EDR plant. American Desalting
Association 1998 North American Biennial Conference and Exhibition, Virginia.
11
World Health Organisation (WHO), 2004.

Guidelines for Drinking-water Quality; Third Edition. WHO, Geneva.
Zakia, A., Bernard, B., Nabil, M., Mohamed T., Stephan, N. and Azzedine, E.,
2001. Fluoride removal from brackish water by electrodialysis. Desalination 133 (2001), 215-233,
Elsevier Science BV.
12
Appendix 1: Fact sheets fluoride removal technologies
1. Nalgonda process
2. Contact precipitation
3. Bone Charcoal
4. Activated Alumina
5. Clay
6. Reverse osmosis
7. Electrodialysis
8. Ion exchange
13
Technology Nalgonda
Process Aluminum sulphate based Coagulation-flocculation sedimentation
Technology The Nalgonda process was adapted and developed in India by the National Environmental Engineering
Description Research Institute (NEERI) and developed to be used at both the community or household levels. The
process is aluminium sulphate based coagulation-flocculation sedimentation, where the dosage is
designed to ensure fluoride removal from the water.
Equipment
The Nalgonda defluoridation as adopted for The Nalgonda technique for domestic and
community
domestic use in the United Republic of Tanzania. defluoridation
Removal The method does not permit sufficient removal of the fluoride, even when appropriate dosage is used.
performance The residual concentration would often be higher than 1 mg/ l, unless the raw water concentration itself
is relatively low.
Scale/flow rate 20-60 litre basket (household)
10-100 litre/h (household)
Experience Established process in India and Tanzania. The aluminium sulphate and lime process was proposed for
defluoridation of water when fluoride in water became a health concern in the USA as the agent behind
mottling of teeth. Four decades later the process was adopted by NEERI as the Nalgonda technique and
developed for low cost use at all levels in India (household, village community and waterworks levels).
Costs Low- costs. See
http://www.who.int/water_sanitation_health/publications/fluoride_drinking_water_full.pdf
Advantages • Widespread knowledge about the possibilities of solving the treatment
problems at different levels, even at very low cost.
• Understanding of the non-stoichiometric co-precipitation mechanisms for
removal of fluoride in the flocculation process.
Disadvantages • The treatment efficiency is limited to about 70 per cent. Thus the process
would be less satisfactory in case of medium to high fluoride contamination in the raw water.
• A large dose of aluminium sulphate, up to 700–1,200 mg l–1, may be needed. Thus it reaches the
threshold where the users start complaining about residual sulphate salinity in the treated water.
• The large dose also results in a large sludge disposal problem in the case of water works treatment.
Contact National Environmental Engineering Research Institute (NEERI) http://www.neeri.res.in/
details/More Fluoride in Drinking water WHO-report:
information http://www.who.int/water_sanitation_health/publications/fluoride_drinking_water_full.pdf
14
Technology Contact precipitation (general)

Process Precipitation
Technology Contact precipitation is a technique by which fluoride is removed from the water through addition of
Description calcium and phosphate compounds and then bringing the water in contact with an already saturated bone
charcoal medium.
Equipment
Contact precipitation for household use Contact precipitation of fluoride as invented in Ngurdoto
Removal > 90% removal of F
performance
Scale/flow rate Several (household, community)
Experience Although it has so far only been implemented at village level in the United Republic of Tanzania and in
Kenya, contact precipitation is probably suitable for implementation at any required level. The figures
show contact precipitation plant as developed for household use and installed at various schools in the
rural areas of the Arusha region, the United Republic of Tanzania.
Costs low
Advantages The process seems to be promising, because it implies:
_ relatively low daily working load;
_ high reliability without the need of surveillance of flow or effluent
concentration;
_ high removal efficiency, even in case of high raw water concentrations;
_ low operating cost; and
_ no health risk in the case of misuse or over-dosage of chemicals.
Disadvantages
Contact Fluoride in Drinking water WHO-report:
details/More http://www.who.int/water_sanitation_health/publications/fluoride_drinking_water_full.pdf
information Household water treatment: http://www.irc.nl/page/8028#fluoride
15
Technology Bone Charcoal

Process adsorption
Technology Bone charcoal is a blackish, porous, granular material. The major components of bone charcoal are
Description calcium phosphate 57–80 per cent, calcium carbonate 6–10 per cent, and activated carbon 7–10 per cent.
In contact with water the bone charcoal is able, to a limited extent, to absorb a wide range of pollutants
such as colour, taste and odour components. Moreover, bone charcoal has the specific ability to take up
fluoride from water.
Equipment
Three most common domestic units for sorption defluoridation [WHO].
The figure above illustrates the three most common types of domestic bone charcoal filters. One of the
differences concerns the water flow in the filter. Another difference between the various configurations is
whether the filter allows the filter medium to drain water, if treated water is withdrawn without ensuring
an adequate influent, allowing the medium to become dry. “Drying” the medium results in disturbance of
the sorption process and more contact time would be required to re-establish treatment. Unfortunately
this point is overlooked in many household filter designs.
Removal Fluoride concentration can be reduced to less than or equal to 1 mg/l
performance
Scale/flow rate 20-60 litre basket (household)
Experience Bone charcoal is the oldest known water defluoridation agent. It was used in USA in the 1940s through
to the 1960s, when bone charcoal was commercially widely available because of its large scale use in the
sugar industry (WHO). The first domestic defluoridators were developed in the early 1960s as column
filters similar to the one shown in the figure above.
Today bone charcoal defluoridation at waterworks has been replaced by the use of ion-exchange resins
and activated alumina. At a domestic level, bone charcoal defluoridation seems to work well in Thailand
and Africa, but so far there is no experience of wide scale implementation.
Costs low
Advantages locally available
simple and easy to build
Disadvantages may give taste; degenerates
not universally accepted
information
16
Technology Activated alumina

Process adsorption
Technology Activated alumina is aluminium oxide (Al2O3) grains prepared to have a sorptive surface. When the
Description water passes through a packed column of activated alumina, pollutants and other components in the
water are adsorbed onto the surface of the grains.
Equipment
column filter household filter
The activated alumina process is carried out in sorption filters as shown in the figure above. In order to
avoid the monitoring of the water quality, the unit is supplied with a water meter allowing for direct
indication of the cumulative water flow. After treatment of, for example, 2,000 litres equivalent to 250
BV of water containing about 5 mg/l, the unit is opened for renewal of the 8 kg of medium. Alternatively
the unit is dismounted for regeneration by the dealer.
Removal According to WHO the fluoride removal capacity of alumina is between 4 and 15 mg g–1. Experience
performance from the field, however, shows that the removal capacity is often about 1 mg g–1 (Fawell et al., 2006).
Thus there seems to be a large difference in the degree of “activation” of alumina products. One of the
explanations may be due to variation in pH. The capacity of alumina is highly dependent on pH, the
optimum being about pH 5.
Scale/flow rate Suitable for both household and community scale
Experience Activated alumina was proposed for defluoridation of water and a drum filter was patented for domestic
use as early as 1936 (WHO). Since then activated alumina has become the subject of several patents and,
due to commercial interests, one of the most advocated defluoridation methods.
The activated alumina process was evaluated for fluoride removal from an underground mine water in
South Africa in the early 1980s and it was found that potable water could be produced from an
underground mine water with a fluoride concentration of approximately 8 mg/l. Two 500 × 103 litres per
day
defluoridation plants were installed as a result of the investigation (WHO-report).
Costs It was previously considered that the activated alumina process, due to high chemical cost and non-
availability in markets, was not a consideration for most developing countries. This is no longer the case.
Experience, mainly from India, Thailand and China, indicates that activated alumina may under certain
conditions
be affordable for low income communities.
Advantages Proven effectiveness, will treat current F and S
Disadvantages Spent regeneration solution contains high F concentrations
Contact http://www.thewaterexchange.net/fluoride-water-filters.htm
details/More http://www.crystalquest.com/data%20sheet%20fluoride.htm
information Fluoride in Drinking water WHO-report:
http://www.who.int/water_sanitation_health/publications/fluoride_drinking_water_full.pdf
17
Technology Clay
Process Adsorption
Technology Clay is an earthy sedimentary material composed mainly of fine particles of hydrous aluminium silicates
Description and other minerals and impurities. Clay is fine-textured, plastic when moist, retains its shape when dried
and sinters hard when fired. These properties are utilized in manufacture of pottery, brick and tile. Both
clay powder and fired clay are capable of sorption of fluoride as well as other pollutants from water.
Equipment
Stratified column of brick chips, pebbles and coconut shells as

used in Sri Lanka.
Domestic clay column filters are normally packed using clay chips found as waste from the manufacture
of brick, pottery or tile. The figure beneath illustrates such a column filter. It resembles the filter used in
Sri Lanka (WHO-report) The filter is based on up-flow in order to allow for settling of suspended solids
within the filter bed. The filter does not have a clean water reservoir and the filtration rate is controlled
by slow withdrawal through the tap.
Removal 60-70%
performance
Scale/flow rate Household scale
Experience According to Fawell et al. (2006) nearly 80 per cent of 600 clay column defluoridators installed in
households in Sri Lanka were found in operating condition after being monitored for different periods
from two years onwards. The described technology was found to be sustainable, but only if the users
were motivated through information and motivation campaigns (Fawell et al., 2006).
Costs low
Advantages locally available
Disadvantages low capacity, slow, low removal efficiency, hygienic aspects because of use of clay
information
18
Technology Reverse osmosis

Process Membrane technology
Technology Reverse osmosis is a membrane technology that uses pressure to force water through a semi-permeable
Description membrane, thereby removing dissolved solutes from solution based on particle size, dielectric
characteristics, and hydrophilic/hydrophobic tendencies. RO can be used as a stand-alone treatment for
most source waters, Beside fluoride molecules also other molecules will be retained. RO is listed as a
fluoride removal BAT (Best Available technique).
Equipment
RO water filter for household Reverse Osmosis Water Filter Diagram
Removal 85-95% removal of F-

performance
Scale/flow rate Varies, there are RO-filters for household use and RO-units for community level
Experience State of the art (small scale and community scale)
Costs Very high
Advantages RO is EPA-listed BAT for both F and As
Familiarity with membrane separation system;
Will treat current (F/As) and possible future contaminants of concern;
Positive public perception
Disadvantages High water loss (20-40%) due to high source water silica concentrations (for RO);
High energy consumption;
High treatment technology capital costs;
Pre- (filtration) and post- (pH/alkalinity adjustment) treatment may be needed;
Chemical handling facilities needed;
Multiple systems needed to achieve water conservation goals (<5% water loss);
Skilled operator required.
Contact www.thewaterexchange.net/fluoride-water-filters.htm
details/More www.crystalquest.com
information
19
Technology Electrodialysis (ED)

Process Membrane proces
Technology Electrodialysis (ED) is a membrane process similar to RO, except that ED uses an applied d.c. potential
Description (electric current), instead of pressure, to separate ionic contaminants from water. Because water does not
physically pass through the membrane in the ED process, particulate matter is not removed. Thus, ED
membranes are not technically considered filters.
The EDR process product water quality is comparable to RO, and may require post-treatment
stabilization. The EDR process is often used in treating brackish water to make it suitable for drinking,
and tends to be most economical for source water TDS levels in excess of 4,000 mg/L.
Equipment
EDR
Removal 85-95% removal of F-
performance
Scale/flow rate Community scale
Experience State of the art technique for brackish water
Costs Very high
Advantages Familiarity with membrane separation system;
Will treat current (F/As) and possible future contaminants of concern;
Positive public perception.
Disadvantages Water loss, high costs, brine discharge, see also disadvantages RO
Contact http://www.gewater.com/index.jsp
details/More
information
20
Technology Ion exchange

Process Ion exchange
Technology The most common ion-exchange removal methods are activated alumina, activated carbon, bone char,
Description granulated bone media, ion exchange resins (defluoron 2) or clay minerals. Ion exchange removal
methods using activated alumina, clay and bone charcoal are described separately.
The water is filtered down trough a column packed with an ion exchange resin. When the adsorbent
becomes saturated with fluoride ions, the filter material has to be back washed with a mild acid or alkali
solution tot clear and regenerate it. The effluent form backwashing is rich in accumulated fluoride and
must be therefore disposed of carefully tot avoid recontamination nearby groundwater.
Equipment
column filter
Removal Medium-high; Depends on quality of water
performance
Scale/flow rate Suitable for both community and household use
Experience Less experience with strong anion-exchange resins because of low capacity and relative high costs
Costs Rel. high
Advantages
Disadvantages High costs, low capacity, sorption of other anions, Fluoride concentration must be less than 10 mg/l.
Contact Resins: http://www.dow.com/
details/More Filters: http://www.ionindia.com/product_range.html
information
21
International Groundwater Resources Assessment Centre
is an initiative of
United Nations Educational, Scientific and Cultural Organization (UNESCO)
World Meteorological Organization (WMO)
is sponsored by
Partners for Water, Government of The Netherlands
is hosted by
TNO Built Environment and Geosciences - Geological Survey of the Netherlands
For more information contact:
IGRAC
P.O. Box 80015
3508 TA Utrecht
The Netherlands
phone: +31 30 256 42 70
fax: +31 30 256 47 55
e-mail: info@igrac.nl
internet: http://www.igrac.nl

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Fluoride in groundwater:

Overview and evaluation of removal

Report nr. SP 2007-1

2 Overview of removal methods .........................................................................................2

3 Setup, scale of use and location .......................................................................................7

Appendix 1: Fact sheets fluoride removal technologies ....................................................13

Fluoride removal methods

1.1 Special projects of IGRAC

1.2 Occurrence of fluoride

1.3 Outline of the report

An evaluation of the methods is given in chapter 4.

2 Overview of removal methods

2.1 Common methods

Adsorption and ion-exchange

Membrane filtration process

Calcium choride x x > 90% possible 1-2% 3 mg CaCl2/mg F 6.5-8

2.2 New technologies

In the reactor fluoride is removed from the water while calcium

Cold feed water takes up heat in the condenser channel

The Memstill® technology can produce (drinking)water at

The WaterPyramid® solution

Source: Aqua-Aero WaterSystems

The Solar Dew Collector system

Source: Solar Dew

Boiling with Brushite and Calcite

New adsorbents for adsorption of fluoride

3 Setup, scale of use and location

Table 2: Differences in characterization of water treatment methods in conventional systems in

General comparison of the methods is given in table 3.

A decision tree for the industrialized countries is shown in figure 1.

A decision tree for the developing countries is shown in figure 2.

Error! Objects cannot be created from editing field codes.

British Geological Survey (BGS), 2003.

Brunt, R., Vasak, L. and Griffioen, J., 2004.

Giesen, A., 1998.

Heidweiller, V.M.L., 1992.

Larsen, M.J. and Pearce, E.I.F., 2002.

Pickard, B. and Bari, M., 2004.

Raichur, A.M. and Basu Jyoti M., 2001.

Solar Dew, 2007.

Werner, T.E. and von Gottberg, A.J.M., 1998.

World Health Organisation (WHO), 2004.

Appendix 1: Fact sheets fluoride removal technologies

Technology Contact precipitation (general)

Technology Bone Charcoal

Three most common domestic units for sorption defluoridation [WHO].

Technology Activated alumina

column filter household filter

Stratified column of brick chips, pebbles and coconut shells as

Technology Reverse osmosis

RO water filter for household Reverse Osmosis Water Filter Diagram

Removal 85-95% removal of F-

Technology Electrodialysis (ED)

Technology Ion exchange

United Nations Educational, Scientific and Cultural Organization (UNESCO)

World Meteorological Organization (WMO)

Partners for Water, Government of The Netherlands

TNO Built Environment and Geosciences - Geological Survey of the Netherlands

For more information contact:

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