Fluoride Waters In Turkey[1]

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Environ Geochem Health (2008) 30: 315-323 Occurrence and Problems of High Fluoride Waters in Turkey - An Overview Nazmi ORUC Eskisehir Environmentai Protection Association (NGO) 2510 F Blok D.8 Yenikent 26050 Eskisehir/TURKEY e-mail: [email protected] ABSTRACT Endemic dental fluorosis was first observed in Turkey in Isparta Province located in SW of Anatolia with mottled enamel related to the high levels of fluoride (1,5-4,0 ppm) in drinking waters about 55 years ago. The origin of fluoride was attributed to the contents of minerals in volcanic rocks, consisting of pyroxene, hornblende, biotite, fluorapatite and glassy groundmass minerals. It was also reported about 35 years ago that severe dental and skeletal fluorosis have been observed in human beings and livestock in Dogubeyazıt and Caldiran areas located around Tendurek Volcano in eastern Turkey where natural waters contained fluoride levels between 2,5-12,5 ppm. It was hypothesed that fluoride which might be transported by fumaroles or escaped from devitrified lavas, could be held on the surface of some minerals and then exchanged with OH - in ground-waters with high pH, at the foothills of young Tendurek Volcano. Endemic dental and skeletal fluorosis was also observed in the inhabitants in Kizilcaoren Village of Beylikova Town in Eskişehir Province situated at the mid-west of Turkey, where the fluoride content of the drinking waters ranged from 3,9 to 4,8 ppm. The origin of high fluoride in the natural waters was related to the fluorspar deposits, occurring in the catchment area near the village. During the survey in the Güllü Village of Esme-Usak, located in south-midwest of Turkey; it was observed that most of the inhabitants born and raised in the village and aged hetween 10 to 30, showed mild to moderate levels of mottled enamel. The fluoride contents of the deep well waters used for drinking in the village, varied from 0,7 to 2,0 ppm. Amorphous microscopic fluorite existing in the Pliocene lake limestones, was considered as a possible origin of fluoride in the waters. Key words: Problems of high fluoride waters in Turkey 1. INTRODUCTION Fluoride is widely distributed in a combined form in several naturally occuring minerals, including fluorite (CaF2), cryolite (Na3AlF6), topaz, tourmaline and micas, in which it is found in combination with silicates, but particularly in association with phosphorus as fluorapatite [Ca5(PO4)3F]. It was estimated that fluoride constitutes about 0,032% of the earth's crust. Because of the wide interest in the relationship of fluorides to general health, an extensive literature is available on high fluoride waters (Edmunds and Smedley, 2005). Except in unusual circumstances, surface waters are generally low in fluoride, the levels being below 1, 0 ppm. On the other hand ground-waters may have greater opportunity to contact appreciable amounts of fluoride depending on geological conditions. Fluoride levels will tend to be higher in alkaline waters and in geothermal areas. In many waters calcium ions are in excess and under these conditions the concentration of fluoride is controlled by CaF2 which at normal temperatures has a solubility of about 15 ppm., and fluoride ion level is limited to about 8 ppm. 1.1 Effects of Fluoride on Human Health : Fundamental information on the relationship fluoride and human health has been very well documented by WHO (Fluoride and Human Health, 1970., Fluorine and Fluorides, 1984). The principal sources of fluoride available to humans are: 1) Water, 1

Transcript of Fluoride Waters In Turkey[1]

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Environ Geochem Health (2008) 30: 315-323

Occurrence and Problems of High Fluoride Waters in Turkey - An Overview

Nazmi ORUC

Eskisehir Environmentai Protection Association (NGO)

2510 F Blok D.8 Yenikent 26050 Eskisehir/TURKEY

e-mail: [email protected]

ABSTRACT

Endemic dental fluorosis was first observed in Turkey in Isparta Province located in SW of Anatolia

with mottled enamel related to the high levels of fluoride (1,5-4,0 ppm) in drinking waters about 55

years ago. The origin of fluoride was attributed to the contents of minerals in volcanic rocks, consisting

of pyroxene, hornblende, biotite, fluorapatite and glassy groundmass minerals. It was also reported

about 35 years ago that severe dental and skeletal fluorosis have been observed in human beings and

livestock in Dogubeyazıt and Caldiran areas located around Tendurek Volcano in eastern Turkey

where natural waters contained fluoride levels between 2,5-12,5 ppm. It was hypothesed that fluoride

which might be transported by fumaroles or escaped from devitrified lavas, could be held on the

surface of some minerals and then exchanged with OH- in ground-waters with high pH, at the foothills

of young Tendurek Volcano. Endemic dental and skeletal fluorosis was also observed in the

inhabitants in Kizilcaoren Village of Beylikova Town in Eskişehir Province situated at the mid-west of

Turkey, where the fluoride content of the drinking waters ranged from 3,9 to 4,8 ppm. The origin of

high fluoride in the natural waters was related to the fluorspar deposits, occurring in the catchment

area near the village.

During the survey in the Güllü Village of Esme-Usak, located in south-midwest of Turkey; it was

observed that most of the inhabitants born and raised in the village and aged hetween 10 to 30,

showed mild to moderate levels of mottled enamel. The fluoride contents of the deep well waters used

for drinking in the village, varied from 0,7 to 2,0 ppm. Amorphous microscopic fluorite existing in the

Pliocene lake limestones, was considered as a possible origin of fluoride in the waters.

Key words: Problems of high fluoride waters in Turkey

1. INTRODUCTION

Fluoride is widely distributed in a combined form in several naturally occuring minerals, including

fluorite (CaF2), cryolite (Na3AlF6), topaz, tourmaline and micas, in which it is found in combination with

silicates, but particularly in association with phosphorus as fluorapatite [Ca5(PO4)3F]. It was estimated

that fluoride constitutes about 0,032% of the earth's crust. Because of the wide interest in the

relationship of fluorides to general health, an extensive literature is available on high fluoride waters

(Edmunds and Smedley, 2005). Except in unusual circumstances, surface waters are generally low in

fluoride, the levels being below 1, 0 ppm. On the other hand ground-waters may have greater

opportunity to contact appreciable amounts of fluoride depending on geological conditions. Fluoride

levels will tend to be higher in alkaline waters and in geothermal areas. In many waters calcium ions

are in excess and under these conditions the concentration of fluoride is controlled by CaF2 which at

normal temperatures has a solubility of about 15 ppm., and fluoride ion level is limited to about 8 ppm.

1.1 Effects of Fluoride on Human Health : Fundamental information on the relationship fluoride and

human health has been very well documented by WHO (Fluoride and Human Health, 1970.,

Fluorine and Fluorides, 1984). The principal sources of fluoride available to humans are: 1) Water,

1

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2) Some species of vegetation, 3) Certain edible marine animals, 4) Dusts in certain parts of the

world, 5) Certain industrial processes. It has been well established that where fluoride occurs in

abnormal amounts in water, chronic endemic fluorosis is likely to exist with the most obvious sign

of mottled enamel of local population. Clinically, mottled teeth are characterized by minute white

flecks, yellow or brown spot areas scattered irregularly over the tooth surface. The chronic toxic

effects of fluoride on the skeletal system have been described from certain geographical regions

of the world, such as India where drinking waters contained high levels of fluoride.

1.2 Effects of Fluoride on Animals: Various sources may contribute to the total fluoride intake of

animals. The most commonly encountered sources of excessive fluoride are: 1) High fluoride water

from natural or industrial sources, 2) Forage subjected to airborne contamination in industrial areas, 3)

Feed supplements and mineral mixtures containing excessive fluoride, 4) Vegetation growing in soils

with high fluoride, and 5) A combination of any or all of these. The most sensitive clinical index of

fluoride absorption is observed as the mottling, staining and excessive wearing of permanent teeth

which were forming at the time of fluoride ingestion. At a more advanced stage of fluorosis, a

distinctive bilateral lameness and stiffness of gait may be observed (Hobbs, et al., 1954, Suttie, 1977).

The main aim of this paper is to summarize the findings of the several researchers who have

conducted several studies on different aspects of high fluoride water problems in Turkey since

1955.

Fig.1 Map of the study areas of endemic fluorosis in Turkey (Tendurek Volcano,Isparta,Eskisehir,Usak)

2. FLUOROSIS IN WATER FROM AREAS OF TURKEY WITH HIGH NATURAL FLUORIDE

2.1 Province of Isparta : Dental fluorosis was observed for the first time about 55 years ago in Isparta

Province, situated at SW of Turkey and related to high fluoride indrinking waters (Ornek, 1955,

Velicangil and Demirhindi,1955, 1957, Ata, 1966). About 100 000 residents

of Isparta city had to use high fluoride waters that contained fluoride levels

between 1,5-6,0 ppm. Usmen (1975) and Samsar (1983) determined the

community index of dental fluorosis (Fci) and the incidence of dental decay

(DMF) on the large number of people living within Isparta city and

surrounding area. It was indicated that in places where high (Fci) values

were found, DMF values were low. A mottled enamel case is given in fig.2.

Oruc and Sansarci (1983) suggested the dilution of high fluoride water with

low fluoride waters to prevent dental fluorosis while supplying enough

2

İSTANBUL

ANKARA

ESKİŞEHİR

ISPARTA

UŞAK

TENDÜREKVOLCANO

Mediterranean Sea

Black Sea

Fig. 2 . Isparta City Centre ( Photo: Oruc,1983 )

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fluoride for the protection against caries. There was no investigation searching the possibilities of the

problems of skeletal fluorosis regarding to the ingestion of high fluoride waters in Isparta. However,

new water was brought from Egirdir Lake to the city center in 1995. With respect to the origin of

fluoride in the waters, several research workers have investigated the relationship between the fluoride

content of these waters and the various rocks in the Golcuk Lake area, located some 6 km. SW of the

Isparta city center (Ozkan, et al., 1988, Bilgin, et al., 1990, Pekdeger, et al., 1990, Ozgur, et al., 1992).

They indicated that Golcuk area consists of sedimentary and volcanic rocks. The volcanic rocks are

tephriphonolite, pyroclastic series and trachyandesite together with trachyite. As fluoride bearing

minerals, the volcanics consist of pyroxene, hornblende, biotite, fluorapatite and glassy groundmass.

The high fluoride content of the drinking water in the city area was related to the dissolution of fluoride

from these fluoride bearing rocks.

2.2 Environs of the Tendurek Volcano: The first report on the results of the analysis of high fluoride

waters and occurrence of fluorosis in humans and animals was prepared by Oruc (1972, 1973, 1976)

following the surveying and analyses of the natural water samples from Dogubeyazit area, located on

the N of Tendurek Volcano in eastern Anatolia. Mottled teeth cases from Tendurek Volcano are

illustrated in Figures of 3 and 4.

Fig. 3. N. of Tendurek Volcano (Photo: Oruc,1972) Fig. 4. S. of Tendurek Volcano (Photo: Oruc, 1976)

Since fluoride toxicity was widely seen in the region, comprising of about 5 000 -10 000 inhabitants

and approximately 40 000-50 000 livestock, several other research workers also conducted many

studies on the endemic fluorosis in the area. Even under the CENTO (Central Treaty Organization)

Scientific Organization)’’ A Seminar on Problems of High Fluoride Waters" was held in Ataturk

University on 6-10 June, 1977 in Erzurum, including a two days field trip in the endemic fluorosis

villages. Key findings from that seminar, are given below:

According to Oruc (1977) seven natural water samples, collected from Dogubeyazit area, contained

excessive amounts of fluoride ranging from 6,5 to 12,5 ppm. The water samples of Caldiran area (S of

Tendurek Volcano) also contained high amounts of fluoride varying between 2,0 and 7,5 ppm. On the

other hand water soluble fluoride determinations were made on soil and plant samples collected from

the fluoride contaminated and control sites around Tendurek Volcano. The fluoride levels of soils taken

from the contaminated and control sites ranged from 1,64 to 13,8 ppm. (median =12.0) and from 0,05

to 0,54 ppm. (median= 0,20), respectively. Analysis of plant samples growing in the fluoride

contaminated areas and control sites showed levels of fluoride ranging from 1,85 to 33,0 ppm.

(median=4,7) and 0,51 to 1,13 ppm. (median= 0,9), respectively. It was concluded that water-borne

fluoride contribution to the water soluble contents of soils had a significant impact on the fluoride

uptake of the plants. In addition to the high uptake of fluoride from drinking waters, livestock grazing in

these areas, could also ingest some fluoride from soils and plants (Oruc, 1977).

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Oktay (1977), concluded that a) high fluoride intake had deleterious effect on skeletal development , b)

this deleterious effect had also occurred, but to a lesser extent on dental tissue. Oztopcular (1977)

examined 29 males and 12 females from the Dogubeyazit villages. In addition to walking difficulties

skeletal changes and changes in tendon reflexes, laboratory findings revealed that chronic fluoride

intoxication caused disturbances in serum electrolytes and in some cases collagen break down

(rheumatoid factor). Electroencephalographic(EEG) activities of the cases studied, showed significant

changes with a tendency towards hypoactive EEG patterns. Figures 5,6 and 7 show skeletal flurosis

cases from N. Tendurek areas.

Fig. 5. A group of patients from N. of Tendurek

Volkano showing O-leg, kyphosis and diffuse

muscular atrophy (From Öztopcular, 1977)

Fig.6. Severe periostal reaction Fig.7. Periostal reactions on the costae, between radius and ulna chalky appearance on the columa

(From Oztopcular, 1977) vertebralis (From Oztopcular,1977)

It was shown by Tuncel (1980) that over the age of 60, patients in the high fluoride group had a

significantly higher incidence of Moenckeberg calcification and there was a highly significant

correlation (p < 0,001) between the severity of these calcifications and severity of the skeletal changes

within the group.

Mermutlu (1977) indicated that the average fluoride levels (w/w) of dental calculus of inhabitants (20 in

each group) aged between 30-40 and 40-60, were 12,4%, and 18.44% from the endemic fluorosis

area, and were 2,72% and 3,53% for the two groups aged 20-40 and 40-60, respectively. Babacan

(1976) showed that chronic fluorosis was detected as a reason for the formation of anaemia both in

the cattle and in sheep with more obvious symptoms in the sheep from Dogubeyazit area. He also

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indicated that as clinical symptoms, pitted and worn teeth and temporary lameness were observed in

the sheep and cattle of the study area.

Sendil and Baysu (1973) first reported the occurrence of fluorosis in humans and animals in the

villages of Muradiye Town in Van Province at eastern Turkey. They indicated that 7 water samples

obtained from the S of Tendurek Volcano and 6 water samples from the N of the volcano, contained

fluoride, ranging from 5,7 to 15,2 ppm. and from 10,3 to 12,5 ppm, respectively. Dental stains and

abrasions, and temporary lameness were detected in sheep, cattle, water buffalo and some horses.

Mottling, staining and abrasions of teeth, arthrosis of joints and stiffness in walking were also observed

in inhabitants of the Caldiran area. Harmful effects of high fluoride on livestock are shown in figures

8,9 and 10.

Fig. 8. Coarsened wool and weakness of a 2 year old Fig. 9. Coarsened hair, dry skin and diarrhoea in a sheep from the Asagiyilanli Village, N. of 4 year old cow from the same village Tendurek Volcana (From Sendil and Baysu, 1973) (From Sendil and Baysu, 1973)

According to the findings of Ergun, et.al., (1987), the

average fluoride concentration of the urine samples from

eastern part (Tendurek Volcano) and western parts of

Turkey (fluoride free areas) in sheep were 8,12 and 1,49

ppm. and in humans 4,32 and 0,99 ppm., respectively.

Also the fluoride concentration in bone, teeth, plant, soil

and water samples from eastern parts were significantly

higher than those of the samples from western of Turkey.

The geological succession of the study area consists of

unexposed Bitlis masif (Paleozoic) metamorphics and

ophiolide overlain by young basaltic lava flows of the

Tendurek Volcano (Olmez, et al., 1994). Natural waters

emerge from these lavas, limestones and marbles in the

flysch and ophiolite rocks. Ten water samples taken from

these natural waters were analysed for chemical

characteristics. High fluoride waters were NaHCO3 type,

and low fluoride waters were Ca-MgHCO3 type. It was hypothised that fluoride which might be

transported by fumaroles or escaped from devitrified lavas, could be held on the surface of some

minerals and then exchanged with OH- ground-waters with high pH. These waters might then

discharge as high fluoride waters from the foothills of Tendurek Volcano (Oruc, et al., 1976).

In another study, 23 samples of natural waters collected from N of Tendurek Volcano were

determined by using potentiometric (fluoride-selective electrode) and spectrophotometric (zirconium-

alizarin) methods. The fluoride contents in these waters generally varied from 0,05 to 13,70 ppm.

Correlation coefficients between the methods used, were found to be statistically significant (Oruc,

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Fig. 10.Excessively worn and broken teeth of a 2 year old sheep from Gökcekaynak Village, N. of Tendurek Volcano (Photo: Oruc,1973)

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1983). A good quality drinking water (Q= 55 1/s) was conveyed to 45 villages from Balikli Lake in last

decades (Oruc, 2001).

2.3 Kizilcaoren Village of Beylikova . Eskisehir : Aksit, et al., (1980) carried out the first field survey

with respect to endemic fluorosis in Kizilcaoren Village, located about 36 km. north of the state road

between Ankara and Eskisehir in central Anatolia. Figure 11 shows mottled enamel case from

Kizilcaoren Village. According to their findings, dental defects were observed in 267 persons (75%) of

the population. All those of seven years of age and above born and raised in the village had dental

problems whereas, the knee, chest and pelvic X-rays in adults showed

evidence of fluorosis and approximately half of the 166 adults (75 or 45,2%)

had advanced fluorosis. It was reported that the fluoride content of the

waters ranged from 3,8 to 4,9 ppm. An extensive epidemiological survey of

the Kizilcaoren area was made by Uslu and Gogus (1981). They examined

157 children, of whom 58% showed typical symptoms of dental fluorosis.

They also observed that the advanced picture of crippling fluorosis was

strikingly uniform among the patients in the village. It was also noticed that

the advanced stage of skeletal fluorosis was the result of continuous

exposure of an individual to high fluoride daily over a period of 10-20 years.

Fluoride content of the drinking waters was reported as ranging from 3,9 to

4,9 ppm. On the other hand Fidanci, et al., (1994) indicated fluoride levels in natural waters varying

from 4,24 to 9,0 ppm around this village. They also noted that new water supplied to the village

contained fluoride between 0,10 to 0,25 ppm. Oruc and Aksit (1989) observed that 10 students among

the 24 elementary school children screened in 1988 still had mottled enamel to varying degrees, since

quantity of the new water supply was not enough especially during the dry seasons, some inhabitants

had to use high fluoride waters again. It was later learned that a good quality spring water has been

supplied to the village since 1992. The Kizilcaoren area is rich in hydrothermal ore deposits which also

formed the alkaline volcanic rocks, situated very close to the south of the village. The ore deposit

contains significant amounts of thorium and rare earth elements as well as fluorspar and barite. Then

the origin of high fluoride in the natural waters was related to the fluorspar ore deposits occurring in

the watershed area of the village (Celik, 1983, Kirikoglu, 1988).

2.4 Gullu Village of Esme, Usak : A study was carried out on the fluoride content of drinking waters

and it’s origin in Gullu Village of Esme Town in Usak Province, located in the mid-west of Anatolia

(Oruc and Vicil, 2001). Fluoride contents of 13 drinking water samples

(mostly deep well waters) varied from 0,7 to 2,0 ppm., (mean=1,35 ,

median=1,60).Fluoride levels were equal or higher than the recommended

limits (1,5 mg/1) set by WHO and Turkish Standarts. During the surveying

of the village, it was observed that about 80% of the inhabitants (total

population was about 1500) born and raised in the village and aged

between 10 and 30 had mottled enamel (dental fluorosis).

pH, Ca++ + Mg++, CO3=, Cl-, SO4

=, Na+ and K+ concentrations of the water

samples were also determined and statistically significant correlations

were found between F- content and Na+ , also negative correlation

between F- and Ca++ + Mg++ concentrations.

The geological survey of the village area and microscopic examination of the rock samples were

carried out to determine the origin of the fluoride. Amorphous microscopic fluorite existing in Pliocene

lake limestones (magnification: x 400) was considered as a possible origin of the fluoride in the deep

well water samples. A new water containing 0.4 ppm. fluoride has been supplied to the village since

1990.

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Fig. 11. Kizilcaoren Village (Photo: Oruc,1989)

Fig. 12. Gullu Village ( Photo: Oruc, 1984)

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According to the study with respect to defluoridation of drinking waters, it was indicated that locally

produced alumina gave promising and economically sound results in terms of defluoridation capacity

and availability in Turkey (Azbar and Turkman, 2000).

CONCLUSIONS

1)Endemic fluorosis that related to high fluoride waters, has been observed in some parts of Turkey,

about 55 years ago. In different parts of Anatolia surface and ground-water samples contained fluoride

between 1,5 to 13.70 ppm.High fluoride concentrations were generally associated with geochemical

formations. Most severe dental and skeletal fluorosis were especially observed in villages in the high

fluoride regions around Tendurek Volcano, effecting human and livestock health.

2)Isparta city center, Kizilcaoren village, Gullu village and 45 villages of Dogubeyazit region (N of

Tendurek Volcano), where varying degrees of dental and skeletal fluorosis existed, have been

supplied with low fluoride drinking waters in the last decades.

3)Low fluoride drinking waters should also be supplied for inhabitants and livestock in Caldiran area

(S. Tendurek Volcano).

Acknowledgements: I would like to thank Fatma BELEN and Fatih INCE for preparation of the

manuscript in digital form.

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