MAWARI - Fluoride Project - MaWaRi.net

MAWARI - Fluoride ProjectProgress Report - 1 st 8 mOrigin, Genesis andDistribution of Fluoridein the Ethiopian RiftDevelopment ofDefluoridationTechnologiesFluoride Research team26 May, 2006Orleans, France____________________________________________________________________Fluoride Origin, Genesis, Distribution and Defluoridation Project - Fluoride Research Team1

Rundown• Introduction• Fluoride Source, Genesis andDistribution Sub-project• Development of DefluoridationTechnologies Sub-project• Training Activities• Purchased Items• Conclusions and Recommendations____________________________________________________________________Fluoride Origin, Genesis, Distribution and Defluoridation Project - Fluoride Research Team2

IntroductionFluorine•Latin "fluofluo" and isolated in 1886 by – HenriMoissan (French Chemist)•The most chemically active non-metallicelement•Occurs naturally in a combined form such as– fluorite, cryolite, apatite•The 17th abundant element in the crust____________________________________________________________________Fluoride Origin, Genesis, Distribution and Defluoridation Project - Fluoride Research Team3

Uses & DrawbacksUsesCFC's such as in Freon, Teflon, lubricating oil, uraniumhexafluoride (gaseous diffusion in atomic power plants)ProblemsOptimum intake 0.5 - 1 mg/L in waters, max 1.5 mg/L (WHO,1996)High fluoride intake results of people are suffering fromDental (1.5-35 mg/L) fluorosis,Skeletal (3.6-10mg/L) and non-skeletal fluorosis andSkeletal crippling (> 10mg/L).____________________________________________________________________Fluoride Origin, Genesis, Distribution and Defluoridation Project - Fluoride Research Team4

Global SenarioMore than 100 million people are at riskof fluorosis, hence fluorosis is a serious aglobal health problem.East African RiftSyria – Mozambique: 4830 km longWidth: a few km – 160 kmArea: 6,500 km2Elevation: 1829 at Kenya – 408 b.s.l. . deadsea____________________________________________________________________Fluoride Origin, Genesis, Distribution and Defluoridation Project - Fluoride Research Team5

Fluoride Project -IntroductionIn this project, effort will bemade to develop:- Defluoridation methods thatutilise locally availablematerials,- Simple to operate,- Household or small communitylevels.Chernet, 1998____________________________________________________________________Fluoride Origin, Genesis, Distribution and Defluoridation Project - Fluoride Research Team8

Structure of the Fluoride ProjectThe Fluoride Project isstructured into two sub-projects, namely,• The Origin and Distribution Fluoride in theEthiopian Rift Valley (Sub-Project 1); and• Defluoridation Techniques (Sub-Project 2).____________________________________________________________________Fluoride Origin, Genesis, Distribution and Defluoridation Project - Fluoride Research Team9

Summary of Duration and Budgetof the Fluoride ProjectNo.Sub-ProjectDurationBudget, EUR1Source, Genesis andDistribution36 months70,390.002Defluoridation Technologies…33 months50,085.00Total120,475.00____________________________________________________________________Fluoride Origin, Genesis, Distribution and Defluoridation Project - Fluoride Research Team10

Personnel involved in the projectOrigin TeamDr. Berhanu Gizaw, GSEMr. Zenaw Tessema, GSEDr. Dereje Ayalew, AAUDr. Tamiru Alemayehu, AAUDefluoridation TeamDr. Feleke Zewge, AAUDr. Nurelegne Tefera, AAUMr. Lemma Dendena, AAUMr. Esayas Alemayehu, Jimma University____________________________________________________________________Fluoride Origin, Genesis, Distribution and Defluoridation Project - Fluoride Research Team11

2. Fluoride Source, Genesis and Distribution Sub-projectThe sub-project investigation focuses on:- Geochemical22- HydrogeologicalFluoride Origin Research Area (1st Phase)- Hydrological37°00'E 38°00'E 39°00'E 40°00'E10°00'NDebreBirhan41°00'E10°00'NLEGENDQuaternary SedimentsQuaternary plateau Volcanics- GeologicalINDEX MAP9°00'NAmboADDISABABADebre ZeytMoj oNazret Awash9°00'NTertiary-Quaternary Rift VolcanicsTertiary plateau BasaltMesozoic SedimentsWolkiteArchean-proterozoic rocks8°00'NZiwayASSELARobe8°00'NIntrusivesGobaLakes0400 800HosainaBekoj iFaultskilometers7°00'NWakaSodo Alaba Kulito ShashemeneAWASADodolaGobaGinir7°00'NRoadTow n Yirga AlemKokosa Research Area WondoDilaYirgachefe0 501006°00'NARBA MINCH KibreMengist6°00'NkilometersGidoleAgere MariamShakisso 37°00'E38°00'E 39°00'E 40°00'ESource: Geological Survey of Ethiopia (GSE)41°00'E____________________________________________________________________Fluoride Origin, Genesis, Distribution and Defluoridation Project - Fluoride Research Team12

2.1 Scheduled Activities for the1st Year- Phase 1 (1st year): Fluoride Distributionmapping in the MER- A literature survey on both locally and abroad(3m: Oct-Dec);- Data collection and compilation work (2m:Jan-Feb)- Data processing; and hydrochemical /groundwater modelling (2m: March-April)- Report writing on surveyed data (5m: May-Sept)____________________________________________________________________Fluoride Origin, Genesis, Distribution and Defluoridation Project - Fluoride Research Team14

No.1234Fluoride Origin Sub-project - Schedule for 1stYearType ofActivityLiteratureSurvey on Fsource &distributionDataCollection /CompilationDataProcessing +1m/m GIS,hydrochemical andgroundwatermodellingtrainingReportWriting /Publishing onthe surveyedDescriptionWorld-wideGSE andothersources2 m/m for 2researchersResearchersandcollaboratorsDuration - One Year: October 2005 - September 2006Oct.Nov.Dec.____________________________________________________________________info / dataFluoride Origin, Genesis, Distribution and Defluoridation Project - Fluoride Research TeamJan.Feb.Mar.Apr.MayJun.Jul.Aug.Sept.15

2.2.1 Local Literature Survey –Done as PlannedPrevious works related to fluoride has beenmade – since 1930's –- Reports bearing fluoride data – numerous-Papers dealing with fluoride ~ 40-Requires more time than planned-Previous studies gave valuable information, butadditional work is required for better understanding of-The source and genesis of high fluoride,-The controlling mineral phase(s) of fluoride and- A clearly distribution trends both in the rock massand in the water bodies.____________________________________________________________________Fluoride Origin, Genesis, Distribution and Defluoridation Project - Fluoride Research Team16

Recharge - Eastern EscarpmentEscarpment____________________________________________________________________Fluoride Origin, Genesis, Distribution and Defluoridation Project - Fluoride Research Team17

Hydrogeology / HydrologyMain aquifer systems in the Rift - fracturedIgnimbrites , Basalts and QuaternarySediments• Recharge are believed to be both fromEastern and Western Escarpment• There exist both saline to good quality watersas well as thermal waters in the system____________________________________________________________________Fluoride Origin, Genesis, Distribution and Defluoridation Project - Fluoride Research Team18

ORIGIN AND DISTRIBUTION OFFLUORIDETHE ETHIOPIAN RIFT VALLEYBased on geological and chemicalinformation - the region may conveniet1y bedivided into two systems, i.e.,The Afar Depression, andThe Main Ethiopian Rift (MER).____________________________________________________________________Fluoride Origin, Genesis, Distribution and Defluoridation Project - Fluoride Research Team19

AFAR DEPRESSION• Dominated bybasaltic volcanism• Waters ofrelatively highsodium chloride, lowFluoride andbicarbonate.THE MER-In general is characterized byacid volcanic rocks- Waters of high sodium,bicarbonate andfluoride concentrations; andnear neutral to alkalinepH.____________________________________________________________________Fluoride Origin, Genesis, Distribution and Defluoridation Project - Fluoride Research Team20

Geothermal Exploration Over 18 potential geothermal areasinvestigated Database available (down to2500m): Geological,geochemical, hydrogeological andgeophysical.____________________________________________________________________Fluoride Origin, Genesis, Distribution and Defluoridation Project - Fluoride Research Team21

NW-SE Geological Section of the Aluto-LanganoRhyolite lava, obsidian & rhyolite b.Gizaw, 1989RhyoliteBasaltIgnimbrite____________________________________________________________________Fluoride Origin, Genesis, Distribution and Defluoridation Project - Fluoride Research Team22

Gas ChemistryWell H2 O2 N2 CO2 H2S NH3 CH4LA-6 0.04 1x10-29 0.25 32 0.2 3.6x10-3 0.13____________________________________________________________________Fluoride Origin, Genesis, Distribution and Defluoridation Project - Fluoride Research Team24

Water Types of the Ethiopian RiftHigh F - dental &skeletal fluorosisNormal F____________________________________________________________________Fluoride Origin, Genesis, Distribution and Defluoridation Project - Fluoride Research Team25

MER Causes of high -Sodium, bicarbonate and fluoride are positively correlatedin the MER waters.Bicarbonate? The reason for the bicarbonate in the area is the highrate of carbon dioxide outgassing.High Fluoride in groundwaters? High CO 2 pressure, 30 bars at 2500mAluto- Langano geothermal Field,? Acid volcanic nature of the rocks,? Geothermal heating, and? Low calcium and low salinity fluids.____________________________________________________________________Fluoride Origin, Genesis, Distribution and Defluoridation Project - Fluoride Research Team26

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CO 2 + H 2 O + Na,K-silHCO 3 + Na, K + H-sil• K-sil + Na Na-sil + K____________________________________________________________________Fluoride Origin, Genesis, Distribution and Defluoridation Project - Fluoride Research Team28

F. Evaporation• Evaporation - major cause of water loss in the Rift• Means of fluoride enrichement____________________________________________________________________Fluoride Origin, Genesis, Distribution and Defluoridation Project - Fluoride Research Team29

AnhydriteSaturation withrespect to Anhydriteand PyritePyriteUnsaturated____________________________________________________________________Fluoride Origin, Genesis, Distribution and Defluoridation Project - Fluoride Research Team30

The State of Fluorite SaturationAluto-LanganoFluorite not a controlling mineral____________________________________________________________________Fluoride Origin, Genesis, Distribution and Defluoridation Project - Fluoride Research Team31

MER Causes of high -Fluoride, salinity and alkalinity in closed-basin lakes? Evaporative concentrationFluoride mobility:LA-8: 2500m 85x? fluoride is a mobile component in acidvolcanic geothermal systems.- The waters areundersaturatedwith respect tofluorite andanhydrite.- Calcium - fixed incalcite and epidote____________________________________________________________________Fluoride Origin, Genesis, Distribution and Defluoridation Project - Fluoride Research Team32

2.2.2 International Literature survey- Delayed from the proposed visit time,October- Underway / in May at Avignon Universityand BRGM- Solubility and related articles ~ 50- Case studies – Countries ~ 70 articlesAustraliaChinaEthiopiaGermanyHungaryIndiaIrelandIsraelItalyKenyaRussiaSenegalTanzaniaUgandaUnited Fluoride statesOrigin, Genesis, Distribution and Defluoridation Project - Fluoride Research Team____________________________________________________________________33

2.2.2 International Literature survey- Periodicals - directly or indirectly dealing with fluoride ~ 70- Internet / Scopus – tens of PDF files- Almost impossible to exhaust - in such a short period of timeand sincesome will be released at a cost- Some sort of leverage is expected in this regard.____________________________________________________________________Fluoride Origin, Genesis, Distribution and Defluoridation Project - Fluoride Research Team34

2.3. Data collection and compilation work(2m: Jan-Feb)- Over the last four decades, the MER - a considerable amount of datahave been collected and archived from hundreds of water points (deepgeothermal wells, boreholes, dug wells, springs, fumaroles,geysersand lakes)- Although data entry from various reports is still underway, data onhundreds of data points have already been entered area wise- Map digitization is simultaneously progressing.____________________________________________________________________Fluoride Origin, Genesis, Distribution and Defluoridation Project - Fluoride Research Team35

2.4. Data processing; and hydrochemical /groundwater modelling (2m: March-April)- Yet to be started____________________________________________________________________Fluoride Origin, Genesis, Distribution and Defluoridation Project - Fluoride Research Team36

3. Development of DefluoridationTechnologies Sub-project3.1 Scheduled activities for the 1st year - undertake:- An assessment of the existing data/information at locally and at theinternational level (3m: Sept. – Nov, 05);- An assessment / Preparation / identification / Characterisation of theavailable materials for defluoridation and estimation of their cost(7m: Oct.05 – April., 06)- Parallel batch defluoridation experiments (4m: April – Jul. 06) )Analysis of the results of batch experiments (3m: June – Aug., 06)____________________________________________________________________Fluoride Origin, Genesis, Distribution and Defluoridation Project - Fluoride Research Team37

An assessment of the existing data/information atlocally & at the international level (3m: Sept. – Nov,05)In this study, an extensive list of treatment options(industrial scale or currently under investigation) has beencompiled and evaluated.- Emphasis was placed on the natural materials and by-products of industrial activities, which may be readilyobtained, employed and disposed of safely.- The study also refined and proposed the types of factorsthat need to be taken into account in deciding on a methodto use for defluoridation for household and smallcommunities scales.____________________________________________________________________Fluoride Origin, Genesis, Distribution and Defluoridation Project - Fluoride Research Team38

Evaluation Results of the AvailableDefluoridationMethods- Chemical precipitation as fluoroapatite may also be a usefulapproach.- Among the several sorbents evaluated, natural clays and relatedminerals are also found to be promising.- Activated alumina, co-precipitation with aluminium sulphate(known asNalgonda Technique), and sorption to bone char -practicedmethod for removing fluoride in developingcountries.- Main disadvantages - these methods require daily maintenance.Furthermore, removal efficiency of the Nalgonda Technique islimited while activated alumina has to be imported and thereforeis more expensive.____________________________________________________________________Fluoride Origin, Genesis, Distribution and Defluoridation Project - Fluoride Research Team39

Evaluation Results of the AvailableDefluoridationMethodsIn Kenya and Tanzania, more than 1,000 householdand 40 communities filters using bone char as a filtermedia. But filtration with bone char has a culturaldrawback.The production of synthetic apatite - could be aninteresting field of research.The research will continue with emphasis on thedevelopment of more cost effective and new fluorideion trap systems.____________________________________________________________________Fluoride Origin, Genesis, Distribution and Defluoridation Project - Fluoride Research Team40

3.1.2 An assessment / Preparation / identification/Characterisation and Cost Estimation(7m: Oct.05 – April., 06)The methods proposed for further investigationand development under this projectinclude:- Aluminium hydroxide and waste residue from alummanufacturing industry;- Iron Oxide; and- Naturally available materials.____________________________________________________________________Fluoride Origin, Genesis, Distribution and Defluoridation Project - Fluoride Research Team41

3.1.3 Parallel batch defluoridation experiments(4m: April – Jul. 06)Based on the identified materials, the following laboratoryactivities are underway:- Development of household defluoridation unit based on aluminiumhydroxide. Continuous column experiments were conducted underdifferent operating conditions and column dimensions and a modelbased on surface reaction rate theory was used to generate the designparameters.- Batch defluoridation experiments are conducted on waste residue fromalum manufacturing industry. The initial result seems highly promissing.- After conducting detailed literature review on naturally available claymaterials, batch defluoridation experiment has been started by usingthese materials.____________________________________________________________________Fluoride Origin, Genesis, Distribution and Defluoridation Project - Fluoride Research Team42

Defluoridation Sub-project - Schedulefor 1st YearNo.Activity2005-091011122006-01020304050607081Assessment of the existing data andinternational bibliography fordefluoridation2Assessment of available materialsfor defluoridation and summarizeestimated cost3Defluoridation materialpreparation/Identification4Characterization of thedefluoridation materials5Parallel batch defluoridationexperiments6Analysis of the results of batchexperiments____________________________________________________________________Fluoride Origin, Genesis, Distribution and Defluoridation Project - Fluoride Research Team43

5. Training ActivitiesMSc LevelOne graduate student is working on development ofhousehold defluoridation unit based on aluminiumhydroxide.Another graduate stuent is currently working onbatch defluoridation experiments on waste residuefrom alum manufacturing industry with modified andunmodified material.A graduate student is also currently finished adetailed literature review work to undertake a batchdefluoridation experiment on naturally availableclay materials.____________________________________________________________________Fluoride Origin, Genesis, Distribution and Defluoridation Project - Fluoride Research Team44

5. Training ActivitiesPh. D. LevelOne Ph.D. student each for the origin and defluoridationresearch are scheduled are under preparation to undertaketheir studies.____________________________________________________________________Fluoride Origin, Genesis, Distribution and Defluoridation Project - Fluoride Research Team45

5. Purchased Items- The team is preparing to look fordealers and suppliers in order to presentpurchase request form for variousfacilities stated in the projectdocument.- So far we only bought computer andrelated facilities, worth of about EUR5,400 worth of 58,000 Birr for the originsub-project.____________________________________________________________________Fluoride Origin, Genesis, Distribution and Defluoridation Project - Fluoride Research Team46

6. Conclusions and Recommendations• The fluoride project is progressing moreor less as planned - with the foreseenproblem of shortage of information fromrecent published articles.• Expected - that the project will beimplemented as per the project document____________________________________________________________________Fluoride Origin, Genesis, Distribution and Defluoridation Project - Fluoride Research Team47

Acknowledgement• French Ministry of ForeignAffairs• Local (Ethiopian) GovernmentInstitutions• CIFEG• Scientific and SteeringCommittee Members• Prof. Yves Travi____________________________________________________________________Fluoride Origin, Genesis, Distribution and Defluoridation Project - Fluoride Research Team48

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