DYE-ASSISTED ANALYSIS OF FLUORINE IN WATER USING UV-VISIBLE

SPECTROPHOTOMETRY

CHAPTER ONE

1.0 INTRODUCTION

1.1 BACKGROUND TO THE STUDY

Fluoride (F-) occurs in almost all waters from trace to high concentration (Dar et al., 2011). It

has been shown to cause significant effects in humans through drinking water (WHO, 2006).

Low concentrations of fluoride in drinking water have been considered beneficial to prevent

dental carries (Maliyekkal et al., 2008; Quin et al., 2009), but excessive exposure to fluoride in

drinking water can give rise to a number of adverse effects (WHO, 2006; Armienta and Segovia,

2008; Aldrees and Al-Manea, 2010; Arveti et al., 2011; Dunne and Verrel, 2011). WHO has set a

limit value of 1.5 mg∙ℓ-1 for fluoride in drinking water (WHO, 2004; Rafique et al., 2008). There

is a narrow margin between the desired and harmful doses of fluoride in drinking water

(Czarnowski et al., 1996; Jha et al., 2011). Therefore, an accurate, simple, rapid and cost-

effective analytical method is of high importance. Spectrophotometric methods are widely used

in the determination of fluoride because of advantages such as simplicity, convenience, accuracy

and reproducibility (Zolgharnein et al., 2009). They are based on the reaction of fluoride with

coloured metal chelate complexes, producing either a mixed-ligand ternary complex or

replacement of the ligand by fluoride to give a colourless metal-fluoride complex and the free

ligand with a colour different to the metal-ligand complex (Einaga and Iwasaki, 1981).

Triphenylmethane (TPM) dyes of most value today are those with auxochromic and

bathochromic groups like amino and hydroxyl in para position to the methane carbon

(Witterholt, 1969). TPM dyes with groups capable of holding metals in stable combination, such
as eriochrome cyanine R and azurol S, have been used successfully as spectrophotometric

reagents for fluoride determination (Thrun, 1950; Macnulty et al., 1956; Sarma, 1964; Dixon,

1970; Einaga and Iwasaki, 1981; Kiernan, 1984). TPM dyes absorb strongly in the visible region

to produce intense, brilliant shades of red, violet, blue, and green (Witterholt, 1969). They are

characterised by high molecular extinction coefficients and by 2 bands in the visible absorption

spectra. The longer wavelength (X band), which corresponds to an oscillation of the charge in

the X direction, is of greater intensity than the shorter-wavelength (Y band), which corresponds

to an oscillation of the charge in the Y direction (Witterholt, 1969; Zollinger, 2003). The present

study aimed to develop spectrophotometric methods for determination of fluoride in the range of

0.0–2.0 mg∙ℓ-1, compatible with the WHO limit value of 1.5 mg∙ℓ-1, using aluminium

complexes of TMP dyes such as chrome azurol B and malachite green as fluoride

spectrophotometric reagents, due to their spectrophotometric properties described above.

Fluoride may be found in drinking water as a natural contaminant or as an additive intended to

provide public health protection from dental caries (artificial water fluoridation). EPA’s drinking

water standards are restrictions on the amount of naturally occurring fluoride allowed in public

water systems, and are not recommendations about the practice of water fluoridation.

Recommendations for water fluoridation were established by the U.S. Public Health Service, and

different considerations were factored into how those guidelines were established.

It is well established that fluoride strengthens tooth enamel and that fluoride prevents caries,

tooth decay, tooth loss, and cavities (e.g., Twetman et al. 2003; Neidell, Herzog, and Glied 2010;

Medjedovic et al. 2015; O’Mullane et al. 2016). The use of fluoride in dental products is

therefore viewed as an important mean to improve dental health. Furthermore, countries such as

Brazil, Malaysia, the United Kingdom, and the United States artificially fluoridate drinking
water for public health reasons so that people are continuously exposed (Mullen 2005). The

Centers for Disease Control and Prevention (CDC 1999) considers water fluoridation as one of

the ten great public health achievements during the 20th century. However, several

epidemiological studies in recent years have found negative associations between fluoride and

cognitive development. Bashash et al. (2017) concluded that children in Mexico had a lower

intelligence quotient (IQ) if their mothers consumed more fluoride during pregnancy. Green et

al. (2019) reached a similar conclusion in their study on Canadian children if the mothers drank

fluoridated water. An increase of 1 milligram of fluoride was associated with a decrease of

almost 4 IQ points, where the overall association was driven by boys. These results have

intensified the debate among scholars regarding whether fluoride is neurotoxic (see Bellinger

2019). After the publication of Green et al. (2019), the American Dental Association released a

statement in which they welcome more studies on the issue (ADA 2019). These findings echo

earlier results of a negative association between fluoride and IQ. A metastudy by Choi et al.

(2012), based on data from China and Iran, concluded that exposure to high doses of fluoride in

water was associated with a reduction of almost a half a standard deviation in IQ among

children. Many of the reviewed papers considered levels that surpass the recommendation from

the World Health Organization that fluoride should not exceed 1.5 milligrams/liter in drinking

water (WHO 2011, 42). However, some of the reviewed studies reported negative associations

with cognitive development for levels below the recommended level. This motivates more

research, given that these levels are present naturally or artificially in drinking water in many

parts of the world. Common problems with the studies reviewed in Choi et al. (2012) are that

they were based on smaller data samples with potentially low data quality.
1.2 STATEMENT OF THE PROBLEM

Fluorine (F) is a univalent poisonous gaseous halogen that occurs under standard conditions

(i.e., room temperature and normal vapor pressure) as a light yellow-green, pungent, acrid gas.

Fluorine has the atomic number 9 and a molecular weight of 18.998 g mol −1. It is the most

electronegative element in the Periodic Table and the most chemically reactive of all elements.

Fluorine readily forms compounds with most other elements, including the noble gases krypton,

xenon and radon. The superb reactivity (i.e., oxidizing capacity) of fluorine is due to its high

electronegativity, its unusually low dissociation energy in relation to other halogens, and the

great bond strength of its compounds. Fluorine compounds are characterized by an oxidation

state −1. In soil, water, plants, foods and even in air, fluorine is present in its ionic form. During

weathering, fluorine can be leached out and dissolved into water, where its natural concentration

depends on the geological, chemical and physical characteristics of the reservoir.

Fluorosis, along with other diseases produced by the intake of fluoride-rich waters, is a major

health concern. Understanding the causes of elevated fluoride concentrations in natural waters is

therefore essential in order to define appropriate protocols of exploitation and management of the

water resources, as well as to design adequate methodologies of remediation. To achieve this

goal, it is necessary to identify the sources of fluorine and the mechanisms that control its

mobility and biodisponibility in natural media.

The problem of the study is the health hazard noticeable among the inhabitants of the study areas

such as dental fluorosis and skeletal deformation which may be traceable to the amount of

fluoride in well water. The prevalence of dental and skeletal fluorosis is not entirely clear. It is

believed that fluorosis affects millions of people around the world, but as regards dental fluorosis

the very mild or mild forms are the most frequent.

1.3 OBJECTIVES OF THE STUDY

1. To know the required dosage of fluoride needed in drinking well water.

2. To know the health implications of the amount of fluoride in drinking well water in Iree

metropolis.

 1.4 JUSTIFICATION OF THE STUDY

Fluoride has beneficial effects on teeth at low concentrations in drinking-water, but excessive

exposure to fluoride in drinking-water, or in combination with exposure to fluoride from other

sources, can give rise to a number of adverse effects such as Dental fluorosis, and skeletal

deformation.

1.5      SCOPE OF THE STUDY

This study is divided into five chapters. Chapter one is the introductory part of the study which

comprises of Problem statement, Research objectives, Justification of the study. Chapter two

covers the review of relevant literature related to the study. Chapter three presents the

methodology and analytical tools used in the study. Chapter four discusses the findings of the

study. Chapter five is the summary of the major findings, conclusions and recommendations.

This project work covers well water from Off-campus, OAU Ile Ife, Osun State and its

metropolis.

 
 CHAPTER TWO

2.0 LITERATURE REVIEW

2.1 SOURCES OF FLUORIDE IN THE ENVIRONMENT

An estimated 70 million people around the world suffer from fluorosis due to chronic exposure

to high levels of fluoride in drinking water. The sources of this element in water are mostly

geogenic, although important contributions also come from industrial activities and coal burning.

Fluorine is the 13th most abundant element in the Earth's crust, as it is contained in several rock-

forming minerals. Among these, micas, apatites and fluorite are the most common minerals

responsible for the release of elevated concentrations of fluoride in natural waters. Fluoride is

also commonly associated with volcanic activity, which on a global scale may release important

amounts of gaseous fluoride compounds to the atmosphere e and produce large deposits of F-rich

lavas and volcanic ashes. The following are the sources of fluoride in the environment

2.1.1 Rock and Minerals

The largest fluoride reserve is considered as the natural input from the rocks and minerals

containing fluoride in there composition Rocks and minerals. Fluoride is one of the most

abundant trace elements in the Earth’s crust, with an average concentration of 625 mg/kg in

different rock types ( Tavener and Clark 2006). The occurence of fluoride varies from one type

of rock to another. Fluoride content range from 100mg/kg in ultramatic rocks and some

limestones to about 1000mg/kg in alkaline igneous rocks and 1300mg/kg in marine shales

(IGRAC 2003) and it has also been reviewed that volcanic rocks produced at a subduction zone

boundary had high valve about 2000mg/kg (Anazawa 2006). This is attributed to differences in

partitioning within the Earth’s crust which help in understanding how fluoride occurs in the
environment. The largest fluoride reserve is the rocks containing fluorine-rich minerals. The

highest fluoride levels are associated with syenites, granites, quartz monzonites, granodiorites,

felsic and biotite gneisses, and alkaline volcanics based on the findings of crystalline igneous

and metamorphic rocks ( Chae et al. 2006, 2007; Ozsvath 2006; Robinson and Kapo 2003; Rosi

et al. 2003). Among all fluoride-rich minerals, fluorite (CaF2), fluoroapatite (Ca5(PO4)3F),

micas, amphiboles, cryolite (Na3AlF6), villiaumite (NaF) and topaz (Al2(SiO4)F2) are

considered as the most abundant minerals which occur primarily in certain igneous and

metamorphic rocks and sediments (Apambire et al. 1997a; Chae et al. 2007; Cronin et al. 2000;

Edmunds and Smedley 2005; Saxena and Ahmed 2003). The granitic rocks containing fluoride

minerals such as amphibolites, pegmatites, hornblende, muscovite and biotite micas supply

fluoride to soils and groundwater by weathering and soil-forming processes. Among the few

laboratory model studies, it has been observed that granites, acid volcanic rocks, basic dikes and

hornblende in gneisses contribute to fluoride-rich soils and waters in the surrounding (Saxena

and Ahmed 2001). Many of the world’s high-fluoride districts are underlain by crystalline

igneous and metamorphic rocks (such as parts of India, Ghana,South Africa) or occur in areas of

volcanic and associated hydrothermal activity. This is due to geochemical behavior of fluorine in

magma. Because fluorine has a higher affinity for silicate melts than solid phases (Anazawa

2006; Sawyer and Oppenheimer 2006). Hence, hydrothermal vein deposits and rocks that

crystallize from highly evolved magmas often contain fluorite, fluorapatite, and fluoride-

enriched amphiboles. Cryolite, villiaumitecan also occur depending on the percentages of silica

and calcium in the magma (Taylor and Fallick 1997; Dolejs and Baker 2004). Thesources of

fluorine in sediments and sedimentary rocks can be attributed to fluoride-bearing minerals

derived from the parent rock, volcanic ash, fluoride-rich clays and fluorapatite (in some
carbonate rocks, phosphate beds, and argillaceous deposits). Often the occurrences of high

dissolved fluoride are associated with high pH in sodium-bicarbonate waters (Chae et al. 2007).

Cryolite Fluorite

Fluorapatite

Minerals

A large number of minerals contain F in their chemical formulas as a primary constituent or

include it as an impurity. Among primary minerals, biotite and muscovite may contain about 1wt

% of F, while contents are higher in accessory minerals, such as fluorapatite (∼3.8 wt%), topaz

(∼11.5 wt%), and fluorite (∼48 wt%). Rare minerals such as cryolite may contain up to 54 wt%

F. Minerals of the apatite group are some of the other important F-bearing minerals associated
with igneous rocks. The apatite-group minerals, which have a general chemical formula, Ca10

(PO4)6X2, include three accepted species: fluorapatite (where X = F), chlorapatite (X = Cl), and

hydroxylapatite (X = OH). Fluorapatite, in particular, is a ubiquitous accessory phase in igneous,

metamorphic, and sedimentary rocks (Pan and Fleet, 2002). Fluorite (CaF2) is a common

mineral that forms in hydrothermal systems usually with a cubic shape but can also form into

octahedral or other suboctahedral shapes, depending on the temperature and composition of the

solution where the crystals grow (Zidarova, 2010). It is also found as a cement in carbonate rocks

(limestones and dolomites), and less often as an accessory mineral in pegmatites and granites or

as a precipitated salt associated with hot springs. Other F-bearing minerals that are much less

abundant include amphiboles (e.g., hornblende, tremolite), topaz (Al2SiO4(OH,F)2), and cryolite

(Na3AlF6).

2.1.2 Geothermal sources

Geothermal waters are associated with active areas of volcanic activity. Geothermal fluids that

rise to the surface include hot water and steam both containing dissolved solutes and gases. They

may be discharged from hot springs, fumaroles, hot-water wells and wet- and dry-steam wells.

Although a small amount of geothermal water may be derived from gases that were originally

dissolved in magmas, most correspond to rainwater that descends through faults to considerable

depths, and then is heated by the magma attaining high temperatures (>250 °C) and pressures.

The most common types of geothermal water are alkali-chloride solutions with near-neutral pH

values (Edmunds and Smedley, 2013), although a great variability in the chemical composition

and in the range of pH can be observed worldwide. Features that are common to most high-

temperature waters include unusually high proportions of Li, Rb, Cs, Si, B, As, F and NH4+. The
concentration of fluoride in geothermal waters is closely linked to the solubility equilibria of

fluorite (Nordstrom and Jenne, 1977), which in turn, also depends on the fluid temperature.

One of the highest dissolved fluoride concentrations measured near the earth’s surface occur in

areas affected by geothermal activity, such as the East African Rift Valley, New Zealand, China,

and parts of the western U.S. For reasons described above (Sect. 2.1.1), highly evolved magmas

and their associated hydrothermal solutions are typically enriched in fluorine. As meteoric waters

come in contact with these types of magma bodies or solutions, they can acquire fluoride up to

the limit imposed by fluorite solubility (Ashley and Burley ; Ayenew 2007 Lottermoser and

Cleverley 2007). Acidic geothermal waters can also contain high fluoride concentrations (Ellis

and Mahon; Nordstrom et al. 2005) but for a different reason. Under low pH conditions, fluoride

solubility is enhanced by the formation of complexes with hydrogen (HFo and HF2-), silicon

(SiF62-), and aluminum (AlFx 3-x), which prevent fluorite from forming. Low pH values

(especially less than 4) also inhibit the precipitation of silicate sinter when geothermal waters

reach the earth’s surface (Nordstrom et al. 2005). This increases the likelihood that fluoride will

remain in the dissolved phase as it is released to the surface environment. Although human

health is not often affected by these types of waters, Heikens et al. (2005) document a case of

endemic dental fluorosis in Indonesia that has resulted from the ingestion of fluoride derived

from a hyperacid volcanic lake.

2.1.3 Food

The fluoride of food items depends upon the fluoride contents of the soil andwater used for

irrigation, and therefore the fluoride content of the food items mayvary from place to place [S.K

Gupta and R.D Deshpande 1998]. Virtually all foodstuffs contain at least traces offluorine. All

vegetation contains some fluoride (Table 1), which is absorbed fromsoil and water. The highest
levels in field-grown vegetables are found in curly kale(up to 40 mg/kg fresh weight). Other

foods containing high levels include fish(0.1–30 mg/kg) and tea. High concentrations in tea can

be caused by high naturalconcentrations in tea plants or by the use of additives during growth or

fermentation.

Levels in dry tea can be 3–300 mg/kg (average 100 mg/kg), so two to three cups oftea contain

approximately 0.4–0.8 mg of fluoride. In areas where water with highfluoride content is used to

prepare tea, the intake via tea can be several times greater (Fawell K. et al.; WHO 2006). The

solubility of fluorapatite (3Ca3(PO4)2_Ca (F, Cl)2) and fluorite (CaF2) in natural waters is very

low. Even in natural waters, on account of the ionic strength of the complex forming ions, the

solubility of CaF2 is further drastically reduced, causing CaF2 precipitation [S.K Gupta and R.D

Deshpande 1998].Fluorine content of plants, mostly cultivated plants, is generally low, except

fortea, which contains up to 440 mg/L fluorine. Sea food contains significantly higher amounts

of fluorine compared to freshwater food [S. Jagtap et al. 2012].

2.1.4 Atmospheric Source

The use of fluorine in industry leads to occupational exposure, e.g., inorganicfluoride compounds

are used in the production of aluminium from cryolite.Fluorides are also released during the

manufacture and use of phosphate fertilizers (S.K Gupta and R.D Deshpande 1998, S. Jagtap et

al. 2012). The importance of fluoride compounds dates back to the time when man first learned

to chemically modify the materials for his environment. Fluoride dust from industry and

industrial plants manufacturing HF acid, aluminium, enamel, and bricks, and industries

consuming high sulfur non-coking coal thermal power plants pollute the environment [S.K

Gupta and R.D Deshpande 1998, S. Jagtap et al. 2012]. The natural sources of fluorine in

precipitation include marine aerosols, volcanic gas emissions, and air-borne soil dust (Angelis
and Legrand 1994; Saether et al. 1995; Tavener and Clark 2006). Efforts to measure fluoride

concentrations in pristine rainfall have been hampered by the nearly ubiquitous presence of

anthropogenic fluoride, but several studies have found that values are typically less than0.08

mg/l unless the precipitation is directly affected by volcanic emissions (Barnard and Nordstrom

1982; Neal 1989; Saether and Andreassen 1989; Cook et al.1991; Edmunds and Smedley 2005;

Tavener and Clark 2006). Even during volcanic eruptions, the resulting plume of HF gas is

quickly depleted from the troposphere through both dry and wet deposition, having only

localized and transient effects on atmospheric chemistry (Angelis and Legrand 1994; Rubinet al.

1994; Aiuppa et al. 2006; Sawyer and Oppenheimer2006). Consequently, natural inputs of

fluoride into the environment from the atmosphere have not been directly linked to human health

problems in the scientific literature. However, there have been cases of acute and chronic

fluorosis occurring in animals that grazed on pastures covered by ash and other particulates from

recent volcanic eruptions (Cronin et al. 2003; Sawyer and Oppenheimer2006) or by dust derived

from phosphate rocks (Cronin et al. 2000).The primary anthropogenic sources of fluorine are

industrial aerosols, which include emissions from brickworks, aluminum smelters, iron and steel

production, fossil fuel burning, ceramic industries and phosphate fertilizers plants (Fuge and

Andrews 1988; Cronin et al. 2000; Feng et al. 2003; Bonvicini et al.2006; Tavener and Clark

2006; Walna et al. 2007). These pollution sources release fluoride to the environment in both

gaseous (e.g., HF, SiF4, F2, and H2SiF4) and particulate forms (e.g., CaF2, NaF, and Na2SiF6).

Atmospheric chlorofluorocarbons also contribute fluoride to rainwater, but the concentrations

(\0.001 mg/l) are insignificant when compared to natural background levels (Sidebottom and

Franklin1996). Rainfall contaminated by industrial emissions can contain fluoride concentrations

that are in order of magnitude greater than background levels, even exceeding 1mg/l (Neal 1989;
Saether and Andreassen 1989; Feng et al. 2003; Walna et al. 2007). There have also been studies

that showed elevated fluoride levels in the bones and antlers of deer living in industrialized

regions of continental Europe (e.g., Machoy et al. 1991; Kierdorf and Kierdorf 2000). Therefore,

although governmental regulatory agencies (such as the U.S. EPA) maintain that current air

quality emission standards are protective of human health, environmental advocacy groups argue

that people living near an industrial source of fluorine emissions face significant health risks

(Griffiths 1992).

2.1.5 Drugs and Organo – fluoride Compounds

Prolonged use of certain drugs has been associated with the chronic adverse effects of fluoride,

e.g., NaF for the treatment of osteoporosis, Niflumic acid for the treatment of rheumatoid

arthritis, and use of fluoride mouth rinse (Proflo) to render the tooth stronger [S.K Gupta and

R.D Deshpande 1998]. The one side effect common to fluorinated drugs is memory loss. Prozac

contains fluorophenyl compounds which contain fluoride and cause liver disease. Prozac can

cause hepatitis and promote tumors in the liver [Anderson J.J et al. 1999].

Organic fluorides are transformed in the liver, and the resulting metabolites can have higher

activity and/or greater toxicity than the original compound. During 1982, two cases of drug-

induced skeletal fluorosis were reported from Switzerland (Jagtap et al. 2012). Organo-fluoride

compounds only rarely release F- under biological conditions and are rarely sources of fluoride

poisoning. In order for fluoride poisoning to occur, a compound must release fluoride (F-) ions.

Whereas most organo-fluoride compounds may not release F, because of the strength of the

carbon–fluorine bond and its tendency to strengthen as more fluorine atoms are added to a

carbon atom, others do, such as methoxyfluoride. The fluorine atom is pervasive in drugs, e.g.,
Prozac and many other substances such as freons (chlorofluorocarbon [CFC]), Teflon [Murphy

C.D 2010], and blood-serum.

A Schematic diagram showing the fluoride existing sources in the environment (Meththika

Vithanage, Prosun Bhattacharya 2015)

2.2 DISTRIBUTION PATTERN OF FLUORIDE IN THE SURFACE AND GROUND

WATER

Fluoride content in drinking water varies around the world depending on the geographical

location. It is estimated that more than 200 million people worldwide rely on drinking water

with fluoride concentrations that exceed the present WHO guideline of 1.5 mg/L (WHO 2004).

A detailed description on the concentration of fluoride in groundwater and its sources in various

regions of the world based on literature (Ayoob and Gupta 2006; Brindha and Elango 2011).

The World Health Organization (WHO) has made 1.5 mg/l as the permissible limit for fluoride

(WHO 2006). Hence the distribution patterns of fluoride in some areas in the world are discussed

below in which most of them has a high concentration above the permissive limit of World

Health Organization.
2.2.1 Southwest region of Nigeria

The analysis of fluoride concentration in the groundwater samples at Abeokuta range from 1.0 to

1.3 mg/l which falls within the basement complex areas. Also, at Ewekoro, fluoride

concentration values ranged from 0.9 to 1.5 mg/l and 0.1–3.2 mg/l in Lagos, which are all

sedimentary aquifers. The maximum value of 3.2 mg/l was obtained from water sample from

Osodi/Isolo area of Lagos, while the least value of 1.0 mg/l was obtained in the water sample

from Surulere area of Lagos metropolis. These concentrations range within maximum accepted

stipulated by WHO expect for those in Osodi/Isolo area of Lagos. Generally, more fluorides are

found in the sedimentary groundwater resources of the study area than in the basement complex

groundwater resources. ( Gbadebo A.M, 2012). The mean values of fluoride (0.56 mg/l) in the

basement complex groundwater resources of the study area (i.e., Abeokuta) fall within the range

of the fluoride values (0.49–0.85 mg/l) obtained in the drinking water from the granitic bedrock

in southern Sweden (Knutsson and Olofsson 2002). Areas of India where Sharma (2003) has

reported cases of dental fluorosis and mottled teeth, The fluoride concentration of 4.1 mg/l

obtained in the groundwater from the wells of Njoro division, Nakuru District of Kenya (Moturi

et al. 2002) is only slightly higher than the fluoride concentration of 3.2 mg/l obtained in the

groundwater resources from Osodi area of Lagos. It is possible that the source of fluoride in the

analyzed groundwater resources from the study area is fluorite (CaF2). The mineral fluorite (i.e.,

calcium fluoride) is normally found in both the sedimentary rock and igneous rocks. According

to this study high concentration of fluoride may have been influenced by the relatively high

ambient temperature and the relatively high TDS which no doubt must have contain the calcium

and magnesium being a limestone region. It can also be attributed to the increasing level of

cement production.
2.2.2 North Nigeria

Fluoride concentration in the basement aquifers ranges from 0.03 to 10.30 mg/L. Forty seven

percent of waters in the basement aquifer fall below the proposed back- ground level of 1.5mg/L

and fifty three percent are above it. Fluoride concentration of 10.30, 7.72 and 8.0 mg/L were

recorded in a well at Langtang and springs at Furzi and Dorong in the north central basement

complex by Dibal H.U 2012,and Lar. U.A, Dibal H.U, Daspan R, Jaryum S.W (2007). In the

northeast basement aquifers, values of 7.00 mg/L were recorded in a borehole and a well each at

Dass by (Izeze E. 2005) and 3.14, 2.97 and 2.25 mg/L in a spring, hand dug well and a borehole

at Dilchidima, Dzuma and Ngalbi (Dibal H.U 2012). Biliri, Kaltungo and Shongwom are other

areas with high values of fluoride concentration. A Hand dug well at Biliri and Kaltungo have

4.00 mg/L of fluoride each in their waters and at Shongwom, 2.36 mg/L of fluoride was recorded

in a hand dug well (Dibal H.U and Lar. U.A 2005). Values of 2.22 and 2.52 mg/L of fluoride

concentration in the northwest basement aquifers were recorded in a hand dug well at Shawo and

Barkin Lamba [Dibal H.U 2012]. Low values of fluoride concentration (0.03 - 0.08 mg/L) were

re- corded in the meta-sedimentary aquifers in the northwest basement areas at Maru in all the

water sources [Dibal H.U 2012].

The sedimentary aquifers have fluoride concentration in the range of 0.00 - 5.00 mg/L. Eighty

nine percent of the waters have fluoride concentration below the pro- posed 1.00 mg/L

background value and eleven percent above it. Three boreholes each at Maiduguri, tapping water

from both the Upper Zone and Lower Zone Aquifer in the Chad Basin have only traces of

fluoride. Value of 0.2 - 5.00 mg/L of fluoride was re- corded in the middle Zone Aquifer by

[Oteze G.E and Ayegbusi M.S 2002]. However, sixty nine water samples analysed by (Barber

W. 1965) recorded fluo-ride ranging from 0.00 - 0.80 mg/L. At Gombe, in the Upper Benue
Basin, fluoride concentration values of 2.10, 2.50 mg/L in two dug wells in the northeast zone

have been recorded [ICOH 2003-2004]. Fluoride concentration value of 1.67 mg/L was recorded

in a borehole at Keana in the Middle Benue Basin (Dibal H.U 2012). The highest value of

fluoride concentration recorded in the northwest sedimentary aquifers is 0.836 mg/L in a hand

dug well (ICOH 2003-2004).

2.2.3 In European environment

The concentration of fluoride in spring and stream waters was used to determine the occurrences

of fluorite in Osor district, Spain (Meththika Vithanage 2015). In Poland, fluoride concentration

of 1.38 mg/L was detected around a phosphate industry waste disposal site (Meththika Vithanage

2015). The fluoride concentrations of about 7 mg/L occur naturally in western Estonia which is

due to Silurian-Ordovician aquifer system (Indermitte et al. 2009). Alumina production plants

had increased the fluoride concentration in nearby soils (0.3–9.2 mg/L) in Greece (Meththika

Vithanage 2015).

2.2.4 African environment

An example from around the world with volcanic activity leading to high-fluoride concentration

in the waters is Tanzania and the area surrounding the East African Rift system. Many of the

lakes in this area have fluoride concentrations reaching up to 1640 and 2800 mg/L (IPCS 2002).

Fluoride contents in some rivers (12–26 mg/L), springs (15–63 mg/L) and alkaline ponds and

lakes (60–690 mg/L) were found to be very high in Tanzania. Meththika Vithanage 2015 noticed

that in natural waters of Kenya, fluoride concentration was greater in lake water than

groundwater and springs which was greater than river water. Evaporation would have been a

major cause to increase the concentration of fluoride in lakes of this region.

2.3 HEALTH EFFECT OF FLUORIDE IN HUMANS

 Fluoride could either be beneficial or detrimental to human depending on the levels it is

consumed in water. A preponderance of evidence reviews the effect of fluoride on human health

of the beneficial effect and adverse effect base on the on the concentration of fluoride in the

water intake.

2.3.1 Beneficial effects

Dental caries remains the most common chronic disease of the childhood in the world, a

preponderance of evidence indicates that moderate levels of fluoride ingestion can reduce the

incidence of dental caries and, under certain conditions, promote the development of strong

bones (Yiming et al. 2001; Rao 2003; Harrison 2005; Edmunds and Smedley 2005; Doull et al.

2006).it also minimize the likelihood of enamel fluorosis. Regular fluoride exposure during the

time of teeth development contributes to long lasting protection against enamel fluorosis and

dental decay. Enamel is a calcium deficiency, carbonate rich hydroxyapatite. It helps to maintain

neutrality and finally leads to the release of calcium from hard tooth substance (Dawes C 2003).

Small amount of fluoride in the solution around the tooth inhibit demineralization more

effectively than incorporate fluoride and have much greater caries – protective potential than the

large portion of fluorohydroxyapatite in enamel which result from the free fluoride ions in

solution around the tooth. Antimicrobial effect can also be found in fluoride. In the laboratory, it

was shown that carbohydrate metabolism of oral streptococci lactobacilli can be inhibited by

fluoride (BalzarEkenback S, Linder L.E, Sund M.L, Lonnies H 2001). In the cell, fluoride can

inhibit two enzymes; enalose and the proton releasing adenosine- triphosphatase (ATPase). The

over acidification of the cytoplasm can also inhibit the mechanism of glucose transport into the

cell.

2.3.2 Adverse effects

The presence of fluoride at elevated concentrations in drinking water has caused severe health

effects in humans in some parts of the world (Bhatnagar et al., 2011; Shen and Schäfer, 2015).

Human disease caused by fluoride manifests itself in some forms: dental, skeletal, non-skeletal

fluorosis and reproductive effects. Apart from teeth and bones, the interaction and involvement

of soft tissues, organs, and other systems of the body with fluoride leads to non-skeletal

fluorosis. It leads to many bone diseases, mottling of teeth, and lesions of the endocrine glands,

thyroid, liver, kidney, and other organs.

Dental fluorosis, the condition which first led to the discovery of a relationship between fluoride

ingestion and human health, is characterized by a mottling of the tooth surface, or enamel. As

enamel develops, there is increased mineralization within the developing tooth accompanied by a

loss of matrix proteins. Exposure to fluoride during this process causes a dose-related disruption

of enamel mineralization resulting in anomalously large gaps in its crystalline structure,

excessive retention of enamel proteins, and increased porosity (Aoba and Fejerskov 2002).

Skeletal fluorosis is characterized by increased bone mass and density, accompanied by a range

in skeletal and joint symptoms. The mechanism(s) that leads to skeletal fluorosis are poorly

understood; however, the stages of development are well-documented (Rao 2003; Susheela

2003; Edmunds and Smedley 2005). In early stages, the symptoms include pain and stiffness in

the backbone, hip region, and joints, accompanied by increased bone density (osteosclerosis).

The stiffness increases steadily until the entire spine becomes one continuous column of bone, a

condition known as ‘‘poker back’’. As this condition progresses, various ligaments of the spine

can also become calcified and ossified. In its most advanced stages, fluorosis produces

neurological defects, muscle wasting, paralysis, crippling deformities of the spine and major
joints, and compression of the spinal cord. The threshold level of fluoride ingestion needed to

cause skeletal fluorosis varies depending on water intake and quality.

Reproductive effects of fluoride on female and male fertility are now considered to be a factor

causing infertility. An epidemiological study review that increase exposure to fluoride may cause

serious toxic effect associated with the increased levels of follicle stimulating hormone and

luteinizing hormone (Ortiz-Perez D., Rodriguez-Martinez M., Martinez F., Borja-Aburto V.H.,

Castelo J., et al. 2003) decrease estrogen levels (Jiang C.X, Fan Q.T, Cheng X.M, Cui L.X

2005) decreased testosterone levels and changes in its conversion into its potent metabolites

(Jiang C.X, et al. 2005), reduced thyroid hormones (Wang H, Yang Z, Zhou B, Goa H, Yan X, et

al. 2009). The most significant of fluoride exposure in male reproduction are changes in the

structure and functional activities of spermatozoa, disruption of spermatogenesis and instabilitiy

of multiple hormone systems (Susheela A.K, Jethanandani P. 1996). Also research shows that

high fluoride in female rat lower pregnancy rate and the number of implantation (Al-Hiyasat A.s,

Elbetieha A.M, Darmanib H 2000).

In Nigeria, the most affected regions with fluoride contamination are the northern and south-

western regions of the country with proportions above WHO discharge limit of 1.5 mg/L

(Akpata et al., 2009). Recently, several researchers have reported high levels of fluoride

pollution in groundwater resources in various locations in Nigeria, in which ninety percent of the

residents depend on for domestic uses (Malum et al., 2019; Emenike et al., 2018a; Emenike et

al., 2018b; Goyit et al., 2018; Bura et al., 2018; Gwaha, 2017; Olasehinde et al., 2016; Okunola

et al., 2016; Dibal et al., 2016; Amadi et al., 2015).

2.5 WHO AND FLUORIDE CONCENTRATION IN PORTABLE WATER

Fluoride occurs in almost all groundwater, there are maximum guideline values for the

concentration of fluoride in potable water, but there are no minimum imposed limits. However,

there are recommended values to ensure there are no potential health risks from lack of fluorides

within the drinking water. WHO places international standards on drinking water which should

be adhered to health purpose. WHO accepted the maximum fluoride concentrations in drinking

water as 1.5 mg/L (Aniruddha Ghosh et al. 2012). The primary controls on dissolved fluoride

concentrations include the types of source minerals, residence time, and climate. However, the

overall water quality (e.g., pH, hardness and ionic strength) also has an important role through its

influence on mineral solubility, complexation, and sorption/exchange reactions (Aniruddha

Ghosh et al. 2012).Primary drinking water standards are those that must be enforced. Secondary

drinking water standards are non-enforceable guidelines regulating contaminants that may cause

cosmetic effects (such as skin or tooth discoloration) or aesthetic effects (such as taste, odor, or

color) in drinking water. In a temperate climate, the recommended levels to help reduce tooth

decay is 1.5 mg/L, while the minimum recommended value is 0.5 mg/L. Fluoride concentration

varied from 0.23–2.03 mg/L with an average concentration of 1.26 mg/L. Most of the water

samples complied with the minimum (0.5 mg/L) and maximum (1.5 mg/L) threshold values for

fluoride in drinking water (WHO 2017).

2.6 ANALYSIS OF FLUORIDE IN WATER

Fluorine is the most electronegative of all elements and occurs primarily as a negatively charged

ion in water. In most potable waters (TDS\500 mg/l), the fluoride ion (F-) comprises over 95% of

the total fluoride present, and the magnesium-fluoride complex (MgF+) is typically the next most

prevalent form (Edmunds and Smedley 2005; Doull et al. 2006). The natural occurrence of
fluoride in groundwater has been reported in many countries of the world with low income

countries being prominent. For instance, 50% of the countries with population consuming water

with fluoride concentration > 1.5 mg/L are from African continent (Kut et al., 2016). The natural

fluoride sources in groundwater are linked to local geological setting of a country which varies

from region to region depending on the heterogeneous rock formations. In Africa, over 435

million people depend on groundwater hosted in Precambrian basement rocks (~220 million),

consolidated sedimentary rocks (~110 million), unconsolidated sedimentary rocks (~60 million)

and young volcanic rocks (45 million) (MacDonald and Davies, 2000). The quality and quantity

of groundwater in these hydrogeological environments is dependent on the physical and

chemical properties of groundwater and host rocks in addition to residence time between the two.

The most reported geological formations with host rocks bearing fluoride minerals include

sellaite, fluorite (CaF2), cryolite (Na3AlF6), fluorapatite (Ca5(PO4)3F), villiaumite (NaF), topaz

(Al2(SiO4)F2), apatite (Ca5(PO4)3F), fluormica, biotite, amphibole and hornblende

[(Ca,Na)2(Mg,F,Al)5(Si,Al)8O22(OH)2] (Brindha and Elango, 2011; Vithanage and

Bhattacharya, 2015). Fluoride contents of African groundwater vary from region to region

depending on the geology, rock types, contact time of the water with aquifer rocks, regional

climate, overall groundwater chemical composition, aquifer depth, and weathering intensity

(Brunt et al., 2004). The highest groundwater fluoride levels generally occur in alkaline volcanic

areas of the East African Rift Valley. The presence of high fluoride concentrations is accelerated

by young volcanic activities, occurrence of thermal waters especially those with high pH, gases

emitted from earth’s crust, granitic and gneissic rocks (Brunt et al., 2004; Malago et al., 2017;

Thole, 2013; Ali et al., 2018, 2019).

2.7 USE OF GIS IN FLUORIDE DISTRIBUTION MAPPING

Due to a large scale of variation in fluoride concentrations controlled by local geology,

topography, climate and physio-chemical properties of water, regional models are required.

Local spatial statistics and GIS (Geographical Information System) tools when integrated

together can provide means of handling large scale of variation in geogenic contaminants. In

addition to characterization of spatial and temporal extent of contamination, local spatial

statistical models indicate significant patterns technically known as contamination hotspots and

cool spots in soil sciences (Zhang et al., 2008; Zhang and McGrath, 2004; Quino Lima et al.,

2020). Several methods for spatial cluster identification are well documented including Gi and

Gi statistics index for temporal clustering, spatial scan statistic (Ishioka et al., 2007) and the

local Moran’s I statistic (J. Ijumulana; F. Ligate; P.Bhattacharya et al, 2020). Due to its

simplicity and ability to test degree of association between individual observation and its

neighbors, the local Moran’s I statistical analysis has been used in several location-based studies

(Nas, 2009; Zhang et al., 2008). However, the results of this technique are highly dependent on

the neighborhood function definition, presence of extreme values and non-normality of the data

values in attribute space (Zhang et al., 2008). The problems can be overcome by adopting

plausible tools such as exploratory spatial data analysis (ESDA) and Geographical Information

Systems (GIS) mapping techniques. ESDA tools provide means of understanding properties of

the data to identify extreme values (spatial outliers) and overall distribution of the dataset in

attribute and geographical space Symanzik, 2014). The GIS mapping capability provides means

of integrating detected hotspots with other spatial datasets and hence facilitates interpretation of

results.
 CHAPTER THREE

3.0 MATERIALS AND METHODS

3.1 DESIGN OF STUDY

This research was designed to study the concentration of fluoride in the groundwater of some

areas at Ile Ife osun state. Four tap water was gotten from different locations at Ashrifa , Moremi,

Modomo and post graduate hall obafemi awolowo university and one well water.

3.2 REAGENT USED AND THEIR SOURCES

The following are the reagent used while carrying out the study and their sources. Distilled water

gotten from chemistry department Obafemi Awolowo University Ife Ile, Sodium fluoride salt

and six different flowers collected at Obafemi Awolowo University campus which are Ixora,

Hibiscus rosa-sinensis, Ceasalphia pulcherima, Delonix regea, Beuihinia monandra and

Hippeastrum eguestre

3.3 COLLECTION, IDENTIFICATION AND PRETREATMENT OF FLOWERS

The flowers were collected from OAU campus premises, it was then took to Herbarium for

identification and authenticated at botany department OAU

Specimen A Specimen B Specimen C

,

3.4 making of flower decoctions

Flowers were collected and sundry for two weeks, it was then grinded using mortar and pestle.

5.00g of the flower was weighed using a high precision balance. A translucent bottle rinsed

properly with ethanol was used to collect the grinded flower and 40ml of ethanol was added to it

for 24hrs and then filtered

3.5 PREPARATION OF STD F- SOLUTIONS

Sodium fluoride salt was used in preparing F- solution

Molar mass of NaF= 23+19= 42g

1ml =1000 µgF-

100ml = 100000µgF- = 0.1gF-

42gNaF =19gF-

X = 0.1gF-

X = 42×0.1/19 = 0.022gNaF

Therfore 0.022g of NaF is dissolved in 100ml of distilled water, hence volume for serial dilution

( 0.1, 0.3, 0.5, 0.7, 0.9, 1.2, 1.5ppm)using 100ml of distilled water was calculated using

C1V1=C2V2

3.6 MONITORING THE UV-VISIBLE ABSORPTIONS OF THE FLOWER

DECOCTIONS

a) Without F- ion (blank) and

(b) With various conntration of F- ions

Specimen A B C
Wavelength 281.0 270.5 275.0
Blank 0.024 0.011 0.072
0.01 0.112 0.077 0.160

0.03 0.093 0.091 0.210

0.05 0.124 0.109 0.120
0.07 0.109 0.120 0.142
0.09 0.139 0.135 0.142
0.12 0.129 0.145 0.147

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