Fluoride Contamination in the Main Ethiopian Rift

Valley
Ines Walther

Heubnerstrasse 11 09599 Freiberg

Abstract: Health diseases occurring due to high fluorine concentrations in drink-

ing water are a widespread problem in the East African rift system including the
Ethiopian Rift Valley. To get information about the fluorine concentrations in
different water sources, samples were taken from rivers, lakes, groundwaters and
hot springs. In this paper sources of high fluoride contents in water should be
introduced, as well as processes leading to them. Furthermore an overview of the
methods for removal of fluorine is given.

Introduction

Fluorine appears in almost every kind of rock, therefore it is exposed to weather-

ing and transport to the surface- and groundwater. The highest concentrations in
fluoride have been recognized in connection with intercontinental hot spots and
along rift zones. In geological instable regions fluorine enriched fluids arise from
the earths crust or mantel to the surface.
In the MER such conditions are recognizable, but the occurring fluorine concen-
trations exceed a lot the common amounts which are known for analogous regions
in other parts of the world. Actually the highest F-content ever measured was
about 2800 mg/L in the rift Lake Nakuru (Kenia). (Kloos, H. and Haimanot, R.T.
1999)
Ethiopia is one of the 23 countries (Nemade, P.D. et al, 2002)where the population
suffers from the consumption of fluorine rich drinking water. Low concentrations
in fluorine in food and drinking water can prevent carries, however uptake of hight
amounts causes severe diseases in teeth and bones, as Fig.1 is shown.
Fluorine substitutes the carbonate component in teeth and bones, therefore the
building of Calogen is hindered which destroys the teeth and bone apatite. Con-
centrations in drinking water above 1.5 mg/L cause dental fluorosis. Prolonged
intake of waters with a fluorine content of 3 to 6 mg/L cause skeletal fluorosis, if
these concentrations are exceeded, crippling skeletal fluorosis occur. (Kloos, H.
and Haimanot, R.T. 1999)
Fig.1: “Pictures of severe dental fluorosis.” All enamel surfaces are affected and present a
corroded-like appearance. (Dean 1942, http://www.fluoridealert.org/dental-fluorosis.htm)

As the intake of amounts of fluorine leads to severe health problems, the World
Health Organisation (WHO) estimates the maximal concentration in fluorine for
drinking water with 1.5 mg/L, the EPA of 2,0 mg/L. However those maxima are
highly estimated. As there are often hot and dry climatic conditions in the con-
cerning regions the daily intake of water and therefore those of fluorine is much
higher. Besides the high fluorine water content leads to accumulation of this halo-
gen in crop and cattle. For that the intake of fluorine is given additionally by sev-
eral sources, like meat and vegetables (Kloos, H. and Haimanot, R.T. 1999).
To solve these problems and prevent the population from health diseases accord-
ing to high fluorine contents in drinking water, it is necessary to get information
about fluorine concentrations in every potential water resource. Besides research
for simple and cheap defluoridation methods should be promoted.

Feature Area

The feature area is situated in the middle of the Ethiopian Rift, in the south of the
Danakilplain. It extends from Metehare / Lake Beseka (east: 39°53’/ nord: 8°55’)
to the south of Nazret and Sodere to the northern shoreline of Lake Ziway ( east.
38°56’ 7 nord: 8°07’).
In Ethiopia there are about 60 million people. An arising amount of them leaves
the rural areas, preferring a life in cities like Nazret and Addis Ababa. These urban
areas often are characterised by population explosion, being unable to provide the
inhabitants with sufficient staple food. Besides nomads and tribes living far from
civilization in the inner country do exist. These are not registered and therefore
information about their supply possibilities is not available.
The Ethiopian Rift Valley grasps an area of about 3300 km². It is part of the big-
gest rift system of the world, with a length of about 6400 km extending from the
eastern part of Jordan to the Coast of Mozambique. Furthermore it has an average
width of about 100 km and divides the whole country from the northeast to the
southwest. On both sides the Ethiopian Plateaus arise to a height of 3000m abso-
lute altitude, however the rift itself is situated on an average of 1000m above sea
level.
50 million years ago the continental plates started to drift apart. The African plate
moves to the northwest, the Arabian one to the southeast. Today the boundary of
both plates appears as rift zone, which is characterized by a low thickness of con-
tinental crust, highly volcanic activity and the occurrence of numerous faults. The
main processes involved in the formation of the MER as it appears today, took
place 2 to 7 million years ago. During that time most volcanoes aroused as well as
the shallow lakes that occur correspondingly to the tectonically conditions, paral-
lel to the faults
The rocks that are found in this area are mainly recent volcanic ones like ignim-
brites, rhyolites, pumices, trachybasalts or fissural basalts, tuffs and obsidians.
Besides there are Quaternary sediments which are transported alluvial and collu-
vial as well as lacustrine. (Reiman, C. et al, 2003)
Water recourses are strongly limited, because the potential evaporation is about
1300 mm/a and therefore higher than the annual precipitation of 1000 mm. Never-
theless there is an annual groundwater recharge of 50 to 150 mm recognizable.
Most aquifers are Pleistocene or Quaternary clefted ones occurring in volcanic
rocks or pore aquifers consisting of Quaternary non consolidated sediments. The
rifted aquifers in the northwest of Nazret up to Metehara show high permeabilities
as well as the pore aquifers between lake Koka and Lake Ziway. All the other
regions do have aquifers characterized by middle permeabilities.
Besides hydrothermalism occurs. Hot springs are situated on the western shoreline
of lake Beseka likewise in Sodere and on the Wonji fault belt. Cold springs appear
around Asela and the Wonji plantation. The quality of water differs a lot depend-
ing on the water source. For “normal” groundwater exists a boundary which runs
about 20km in the north of lake Ziway. It separates groundwater from the north
that is high in salinity (TDS: 1000 – 3000 ppm) from that of the south that shows
lower contents in total dissolved salinity TDS: 500 – 2000ppm). In general hydro-
thermal waters have high salinity as well as pH values.
As main surface water bodies the Lakes Koka, Ziway and Beseka and also the
river Awash should be mentioned.

Sources of high fluoride content in water recourses of the Main

Ethiopian Rift

The occurrence of fluorine generally depends on the type and composition of

bedrock, the existence of hydrothermalism, atmospheric deposition and anthropo-
genic sources.
There are about 150 fluoride bearing minerals however villiaumite, fluorospars,
flourapatile and cryolite are the most abundant ones. Many rocks of the rift are
enriched in those minerals. Especially amorphous rocks, like pumice, tuffs, pyro-
clastics and porphyry or other easily weatherable materials, like volcanic ash or
sediments of salt lakes are concerned by washing out the fluorine component into
the surface- and groundwater. Leaching out the fluoride from easily weatherable
volcanic rocks is thought to be the main source of high fluoride levels in water
recourses of that area. This process is promoted by hydrothermal waters. Both
high temperatures and long contact times of water and rocks lead to higher solu-
tion effects of the soluble fluorine bearing minerals like fluorite. Otherwise the
formation of calcite is promoted by higher temperatures, so that additionally the
content in free calcium decreases with an increase in temperature.
Because of arid climatic conditions the building of evaporates occurs in the near
of the salt lake Beseka. Those rocks are highly enriched in salt and therefore in
fluorine too. Fluoride is transported by the rise of soil water to the earths surface.
It accumulates until it is washed out by precipitation into the surface- and
groundwater.
The input of fluoride into the rift waters that is caused by atmospheric deposition
or anthropogenic influences can be ignored. Fluoride producing industry is not
settled in that region. The only anthropogenic source could be fluorine bearing
fertilizer or pesticides as well as disinfectant used in agriculture. (Mwede, E.,
2000, p 95)

Results

Obviously water from different sources shows a big difference among the fluorine
values. This is visualized in Fig.2, where the water sample points are drawn on the
hydrogeological map of Ethiopia. The points are distinguished among waters from
rivers, lakes, groundwater and hot springs. The concentration of fluorine is sym-
bolized by different colours.
Fig.2: Sample area and sample points of different water sources showing their fluorine
content.

The fluorine contents in rivers are very low, due to dilution effects caused by
precipitation. It is almost the same concentration of about 1mg/L, that can be mea-
sured in streams.
As expected the groundwaters, especially hot springs are richer in fluorine, be-
sides they show a varying in fluorine content from 1 to 14 mg/L. This enrichment
can be explained by longer contact times between rocks and water, higher tem-
peratures and high pH values, which avoid the formation of fluorine complexes on
the one hand and provide the fixation of calcium in calcium carbonates on the
other hand. Both leads to a higher content in free fluoride.
Lakes like Ziway and Koka often show low fluorine concentrations in the same
order of magnitude as rivers. However the situation is different in salt lakes like
Beseka. There concentrations of about 30 mg/L up to 62mg/L at the shallow
shoreline have been measured. In the rift, salty lakes generally show the highest
fluorine values.
Two processes are involved in generating these high levels. First should be men-
tioned the high pH-values of about 9,3 and therefore the high content in Carbon-
ate. Modelling with PHREEQC has shown that the total amount of Calcium is
7.581e-05 moles/L but 5.135e-05 moles/L are fixed in calcium carbonate, so only
1.912e-05 moles/L occur as free Calcium being able to fix the fluoride. In general
the investigated waters are dominated in hydrogen carbonate as it is visible in
(Fig.3.). Therefore it is enough carbonate present to fix the calcium. Nevertheless
the highest amount of calcium occurs as free ion, apart from the one in lake Be-
seka where the most calcium is fixed in calciumcarbonate.
percentage amount of ion on the

100%

80%
HCO3-
cationcontent

60% sulfate
nitrate
40%
chloride
20% fluoride

0%

) ka on S) ) ) ka g) sh )
ni rm m W
(GW ese tati e (H (Do ll fa far Ko prin wa (G
a B n r e r e s A ji
an ke pla ode sh 1 W (nea Lak hot on
o nd La ash S a 4 ji (
lW
G w h n el
ra Aw A as W
o W
Au Aw
sample

Fig.3: Distribution of Anions as a percentage. Almost all samples show a content of unless
60% in hydrogen carbonate.
The second process is connected to the high evaporation rates in the arid feature
area, which cause an accumulation of saline components, including fluorine. This
also is recognizable in high conductivity values and also in high contents of so-
dium, potassium and chlorine of the investigated water samples.

1,600E-03
1,400E-03
1,200E-03 concentration
1,000E-03 [mol/L]
8,000E-04
6,000E-04
4,000E-04 Ca2+ [mol/L]
2,000E-04 F-(frei)[mol/L]
0,000E+00
Aura Gondana

Lake Beseka
Awash plantation

Ca2+ [mol/L]
Sodere (HS)
Awash 1 (Doni)

Awash 4 (near farm)

Well farm

Wonji (hot spring)

Lake Koka
(GW)

Well Wonji (GW)

Awash

featurename

Fig.4: Occurrence of free calcium and fluorine (modelled with PHREEQC)

Figure 4 shows the content of free available calcium and fluorine in different
water samples, modelled with PHREEQC. Obviously the fluorine content de-
creases by an increasing amount of calcium due to the precipitation of both com-
ponents. If there is enough calcium as free ion available the solubility of fluorine
is restricted. Actually the contents in calcium are low and did usually not exceed a
level of about 3 mg/L. Volcanic, and granite rocks in special, do not contain high
amounts in calcium, that is why the waters also show these low concentrations.

Methods for defluoridation of drinking water

Research in methods for defluoridation of drinking water have been done since
1930 without success. Actually there is no world wide accepted defluoridation
method, which fulfils all requirements as there are efficiency, selectivity, low
costs, easy treatment and the avoiding of negative side-effects connected to the
fluoride removal.
All methods for the treatment of drinking water are based on the adsorption prop-
erties or the precipitation reaction of this halogen. The precipitation of fluorine
with calcium by giving gypsum into the untreated water did not lead to acceptable
fluoride concentrations for drinking water. Furthermore fluoride removal was
tested by adsorbing it with different materials like cattle bones, clay enriched in
aluminium and iron oxides (e.g. Ando soil), plants (e.g. Moringa oleifera), lime-
stone, serpentine and charcoal. Cheap and easily available materials often did not
match the desirable fluoride levels or lead to a bad taste in water, especially when
cattle bones were used. Methods of high efficiency often are very expensive. Be-
sides the water quality can become worse when metal ions (iron or aluminium) are
mobilized during ion exchange reactions.
At the end of the 90ees a project concerning the treatment of drinking water has
come into being by governmental support in and around Nazret. About 10% of the
rift population profit from this project. This indicates that huge projects concer-
ning the removal of fluoride in drinking water do not have to reach similarly a
high amount of people. Instead of this, easy treatable, cheap and flexible applica-
ble techniques have to be developed and provided for the population of rural and
urban areas.(Kloos, H. and Haimanot, R.T. 1999)

Conclusion

So far the reasons for high fluorine concentrations in water and the processes
leading to them are well understood. However there is no satisfactory theory ex-
plaining the enormous concentrations in fluorine compared to those of regions
with analogous geological properties.
Also health diseases from which the concerning population is suffering are com-
monly known. In contrast the possibilities to solve these problems are rare.
Considering only the fluorine contamination, it would be advisable to prefer sur-
facewater from rivers and sweetwater lakes for drinking purposes. Otherwise
rivers often are used as sewage systems and may be therefore polluted with bacte-
rial or other pollutants.
Another possibility would be the mixing of water from different sources. For ex-
ample watercourse from the Awash could be chosen to mix it with that one from
wells at the Wonji fault belt. Besides it is possible first to use an easy, cheap
method which is less effective to mix this treated water afterwards with water low
in fluorine content.
To prevent people from using fluorine contaminated water it is necessary to pro-
vide enough drinking water for them. At the moment the natural occurring water
resources cannot fulfil the needs of the population. Rainwatercatchments cannot
be used the whole year. Wells and boreholes which were build often do not work
or contain water in bad quality. As long as the population is suffering from
drought, the main problem will be seen in water quantity. Therefore people prefer
health risks in drinking polluted water instead of dying from drought.
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http://www.fluoridealert.org/dental-fluorosis.htm (picture reference)