Distribution of uranium and thorium in Timahdit s Moroccan black shale

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1 Distribution of uranium and thorium in Timahdit s Moroccan black shale C. Galindo, L. Mougin, S. Fakhi, A. Nourreddine Institut Pluridisciplinaire Hubert Curien Strasbourg, France Laboratoire de Radiochimie (LRC) Faculté des Sciences Ben M sikm sik,, Casablanca, Morocco niversité Hassan II Mohammedia ires.in2p3.fr Catherine Galindo RadChem

2 Outline Context Mineralogical characterization of the black shale SEM, XRD Radiochemical analysis of the black shale Raw material Results of sequential extractions Conclusion

3 Introduction Black shales new adsorbents removal of organic substances, heavy metals and bacterium removal of radionuclides (,Th) Radioactive elements more concentrated in black shales than in other sedimentary lithologies Release of, Th into the ecosystem during thermal processing or chemical activation Purpose of the present work: To To define the modes of occurrence of and Th in the raw material. Catherine Galindo RadChem

4 Timahdit s s black shale MEDITERRANEAN SEA ATLANTIC OCEAN Origin: the Maastrichtian age This deposit is a vein of schist m thick The studied layer is the richest in organic matter (17%: kerogen, humic acids) Catherine Galindo RadChem

5 Mineralogical characterization of the black shale (SEM, XRD) Clays (illite, kaolinite, smectite) illite Quartz Dolomite Calcite Hydroxy-apatite Pyrite framboidal and euhedral forms No iron or manganese oxyhydroxides Catherine Galindo RadChem

6 Radiochemical analysis & Experimental procedure Radiochemical analysis & Experimental procedure raw material (1g) calcination fusion (NaOH/Na 2 O 2 ) coprecipitation (Fe(OH) 3 ) AG1X4 resin 10M HCl 1M HNO 3 AG1MP1 resin teva resin Th 8M HNO 3 (wastes) 2M HNO 3 (wastes) 10 M HCl teva resin 0.01M HNO 3 2M HNO 3 (wastes) 5M HCl electrodeposition PIPS detectors α-counting FWHM = 25 kev Catherine Galindo RadChem

7 Radiochemical analysis of the raw material Radiochemical analysis of the raw material Th from continental landmass Bq.kg detrital ,9 19,5 authigenic Th 232 Th 228 Th Authigenic uranium: [ a [ Th] ] = [ ] 3 a = 96% of the total uranium deposition under reducing conditions Wignall P.B., Meyers K.J., 1988, Geology, 16, Catherine Galindo RadChem

8 raw material Sequential extractions raw material F1 F2 F3 F4 F5 F6 deionised water 1M MgCl 2 CH 3 COONa - ph = 4, M NH 2 OH,HCl, 25% CH 3 COOH H 2 O 2 HNO 3 -ph =2 residue water soluble fraction Exchangeable fraction Bond to carbonates Bond to iron oxyhydroxides Bond to apatite Bond to organic matter and accessory minerals Bond to silicates and Th measurement [calcination] [fusion (NaOH/Na 2 O 2 )] coprecipitation (Fe(OH) 3 ) AG1MP1 resin teva resin AG1X4 resin teva resin electrodeposition Solid/solution : 1/10 α-counting Catherine Galindo RadChem Th HCl + HF residu Bond to humic acids, carbonates, silicates Bond to kerogen / pyrite

9 Results of sequential extractions Results of sequential extractions F1 F2 F3 raw material water soluble fraction exchangeable fraction carbonates Distribution of in the black shale 100,00 % 75,00 F4 F5 apatite organic + pyrite 50,00 25, kerogen + pyrite : 3% F6 silicates 0,00 F1 F2 F3 F4 F5 F6 HCl + HF water-soluble organic complexes : < 1 % Silicates : 3% Carbonates : 10% Apatite : 8% Organic matter (humic acids) : 75 % Catherine Galindo RadChem

10 Results of sequential extractions Results of sequential extractions Mobilization of 234 % 100,00 «organic» fraction ,00 50, Activity (Bq) ,00 0,00 F1 F2 F3 F4 F5 F6 HCl + HF Th 20 carbonates Carbonates Apatite 15 apatite Activité (Bq.kg -1 ) Activité (Bq.kg -1 ) Catherine Galindo RadChem

11 Results of sequential extractions Results of sequential extractions Distribution of 232 Th in the black shale 232 Th : detrital input raw material % Th F1 water soluble fraction 75 F2 F3 F4 exchangeable fraction carbonates apatite carbonates, apatite : A232 Th < DL F1 F2 F3 F4 F5 F6 HCl + HF F5 F6 organic + pyrite silicates Silicates : 49% kerogen + accessory minerals: 51% Catherine Galindo RadChem

12 Conclusion Characterization of a Timahdit s black shale in terms of, 234, 235, 232 Th, 228 Th, 230 Th repartition Deposition under anoxic environment Distribution: humic acids 232 Th silicate minerals and pyrite Chemical behaviour of and Th, alpha decay related processes are widely responsible for disequilibria in the uranium decay series Catherine Galindo RadChem

13 Catherine Galindo RadChem

in2p , version 1-27 Feb 2007

in2p , version 1-27 Feb 2007 Author manuscript, published in "Journal of Environmental Radioactivity 92 (2007) 41-54" DOI : 10.1016/j.jenvrad.2006.09.005 DISTRIBUTION OF NATURALLY OCCURRING RADIONUCLIDES (U, Th) IN TIMAHDIT S BLACK

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