HYDROGEOCHEMICAL AND ISOTOPIC STUDY OF GROUNDWATER APPLIED IN ENVIRONMENTAL REMEDIATION URANIUM MINE OSAMU UTSUMI/INB

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HYDROGEOCHEMICAL AND ISOTOPIC STUDY OF GROUNDWATER APPLIED IN ENVIRONMENTAL REMEDIATION URANIUM MINE OSAMU UTSUMI/INB Heber Luiz Caponi Alberti ab, Sueli Yoshinaga Pereira b, Ricardo Perobelli Borba b, Peter Marshal Fleming c ; Ricardo Tadashi Goda a, Marina de Sá Antunes a ; Antônio Ídolo Dias a, Fabio William Rodrigues d UNICAMP - Universidade Estadual de Campinas/SP Brazil CNEN/LAPOC - Comissão Nacional de Energia Nuclear - Poços de Caldas/MG Brazil. CNEN/CDTN - Comissão Nacional de Energia Nuclear - Belo Horizonte/MG Brazil. INB - Industrias Nucleares do Brasil - UTM/Caldas

Objectives 1.Site Characterization 2.Chemical characterization of groundwater 3.Determination most important geochemical processes between rock / water. 4.Classification and separate types of aquifers 5.Behavior of chemical species 6.Develop a conceptual model Hydrogeochemical

Methods 1 - Geoprocessing and mapping Model Digital Elevation Geological Map Radiometric Map 2 Groundwater sampling Low flow pumping 3 Hydrodinamic Potentiometric Map Hydraulic Condutivity Map 4 Hydrochemistry piper and stiff Multivariate analysis Radioactivity and Radon Environmental isotopes O/D and Tritium Sulfur isotopes 5 - Hidrogeochemistry Conceptual Model

5 - Hidrogeochemistry Conceptual Model The hydrogeochemical models attempt to understand and represent chemical dynamics applied to geological systems and the rock-water interaction (Nordstrom& Campbell, 2014). interpretation or predictions Why build a hydrogeochemistry conceptual model? understand the behaviour of the aquifer and systematize information. guide remediation projects showing priority areas.

1 - Geoprocessing and mapping

Model Digital Elevation Before mining Elevation - Meters 1470.5-1500 1441-1470.5 1411.5-1441 1382-1411.5 1352.5-1382 1323-1352.5 1293.5-1323 1264-1293.5 1234.5-1264 1205-1234.5

Model Digital Elevation After mining Elevation - Meters 1470.5-1500 1441-1470.5 1411.5-1441 1382-1411.5 1352.5-1382 1323-1352.5 1293.5-1323 1264-1293.5 1234.5-1264 1205-1234.5

Geological Map

Geochemistry of Rocks

Mineral Balance

Using a mobile radioactivity system (scintillation detector and GPS)

Radiometric Map

3 Hydrodinamic

Potentiometric Map Water level

Hydraulic Condutivity Method

Hydraulic Condutivity Map

4 Hydrochemistry

major cations

major anions

major metals

Grouping and classification of groundwater

Cluster analysis - grouping Dendrograma Ligação Completa. Distância de Pearson 0,00 Similaridade 33,33 66,67 100,00 P1 P33 P10 P30 P16 P CONSULTA P36 P37 P35 P39 P BNF P CAVA Observações P41 P19 P34 P40 P42 P44 P43 P38 Gráfico de escores de ph.... Mn 5 4 P38 C19 1 2 3 4 Segundo Componente 3 2 1 0-1 -2 P43 P42 P40 P44 P41 P19 P34 P CONSULTA P36 P30 P39 P37 P35 P10 P16 P BNF P CAVA P1 P33-3 -2 0 2 4 6 Primeiro Componente 8 10

Piper diagrams

Water classification Amostra Campanha 1 Campanha 2 Campanha 3 P1 Cálcica Sulfatada Cálcica Sulfatada Cálcica Sulfatada P10 Cálcica Sulfatada Cálcica Sulfatada Cálcica Sulfatada P16 Cálcica Sulfatada Cálcica Sulfatada Mista Sulfatada P19 Sódica Bicarbonatada Sódica Bicarbonatada Sódica Bicarbonatada P30 Mista Sulfatada Cálcica Sulfatada Mista Sulfatada P33 Cálcica Sulfatada Cálcica Sulfatada Cálcica Sulfatada P34 Cálcica Sulfatada Cálcica Sulfatada Cálcica Sulfatada P35 Cálcica Sulfatada Cálcica Sulfatada Cálcica Sulfatada P36 Sódica Sulfatada Sódica Sulfatada Sódica Sulfatada P37 Sódica Mista Sódica Bicarbonatada Sódica Bicarbonatada P38 Cálcica Sulfatada Cálcica Sulfatada Cálcica Sulfatada P39 Cálcica Sulfatada Cálcica Sulfatada Cálcica Sulfatada P40 Cálcica Sulfatada Cálcica Sulfatada Cálcica Sulfatada P41 Cálcica Sulfatada Cálcica Sulfatada Cálcica Sulfatada P42 Cálcica Sulfatada Cálcica Sulfatada Cálcica Sulfatada P43 Mista Bicarbonatada Cálcica Bicarbonatada Sódica Bicarbonatada P44 Cálcica Sulfatada Cálcica Sulfatada Cálcica Sulfatada Cava Cálcica Sulfatada Cálcica Sulfatada Cálcica Sulfatada BNF Cálcica Sulfatada Cálcica Sulfatada Cálcica Sulfatada Consulta Sódica Bicarbonatada Cálcica Bicarbonatada Sódica Bicarbonatada

Environmental isotopes applied in hydrogeology

Radioactivity and Radon - 222 Rn The concentrations of radon dependent basically the concentrations of Uranium and Radio in the rock Some studies using radon as a environmental tracer for estimation groundwater flow velocities in single-well test. HAMADA (2000) and Schubertet.al (2010).

Total water radioactivity (U, Th, 228 Ra, 226 Ra, 210 Pb)

Radon - 222 Rn (Radiation Monitoring ALPHAGUARD)

Dating groundwater / Tritium H 3 Wells 1 10 16 19 30 33 34 35 36 37 38 39 40 41 42 43 44 Cava BNF Consulta UT 1.41 2.09 1.69 1.65 1.44 1.91 1.67 1.86 2.00 1.92 1.70 1.92 0.37 1.45 1.93 1.61 1.40 1.85 1.81 2.16 Concentrations of tritium estimated for rainfall in Brazil

isotopes of oxygen and hydrogen - 18 O/ 2 H

The isotopic signature SULFUR Atmospheric oxygen δ 18 O = 23,5 Dissolved oxygen water δ 18 O = -12 e -4 Oxygen in the sulfate - Groundwater δ 18 O SO 4 = -4.4 a -1,0 Sulphur - Rocks δ 34 S SO 4 = -3,63 a +1,24 Sulphur - Sediment δ 34 S SO 4 = -23 Sulphur - Groundwater δ 34 S SO 4 =-3.06 a -0,31

Sulfur isotopes Poços SO 4 (mg/l) δ 34 S SO4 δ 18 O SO4 δ 18 O H2O x 1-x 1 4339.0-2.79-1.0-7.0 0.50 0.50 10 34.3-1.56-2.1-6.7 0.59 0.49 16 19.1-1.40-4.0-7.0 0.92 0.08 19 <0,5-7.2 30 33.1-1.28-3.0-7.0 0.84 0.16 33 7796.6-1.85-3.5-6.1 0.74 0.26 34 163.6-2.77-3.9-5.2 0.86 0.14 35 53.2-6.4 36 10.8-1.79-6.9 37 <0,5-7.0 38 172.0-3.28-2.4-6.8 0.62 0.38 39 264.8-1.99-2.9-6.1 0.73 0.27 40 398.3-2.56-3.3-7.5 0.63 0.37 41 944.9-2.90-1.4-7.5 0.48 0.52 42 72.1-3.72-4.3-7.3 0.72 0.28 43 0.8-2.04-3.4-7.3 0.65 0.35 44 68.6-7.3 Cava 991.5-0.31-3.5-4.5 0.90 0.10 BNF 415.3-3.06-4.4-6.9 0.76 0.24 Consulta <0,5-5.6 (X) The oxidation of the pyrite due to the oxygen present on the water (1-X) The oxidation of the pyrite by oxygen in the air

Main chemical species and chemical complexs PHREEQC Elemento Espécie Espécie Espécie Química Elemento Química Elemento Química Ca Ca+2 N(5) NO3- U6 UO2SO4 CaSO4 CaNO3+ UO2+2 K K+ Al AlSO4+ Y Y+3 KSO4- AlF+2 YSO4+ Na Na+ Fe+2 Fe+2 Sr Sr+2 NaSO4- FeSO4 SrSO4 Si SiO2 Fe+3 Fe(OH)3 Ba Ba+2 HSiO3- Fe+3 BaNO3+ Mg Mg+2 Mn Mn+2 Cd Cd+2 MgSO4 MnSO4 CdSO4 S(6) SO4-2 Zn Zn+2 Pb Pb+2 AlSO4+ ZnSO4 PbNO3+ F AlF+2 U4 U(OH)4 F- UF3+

U(6)/U(4) Fe(3)/Fe(2) Campanha 1 Campanha 2 Campanha 3 Campanha 1 Campanha 2 Campanha 3 P1 2,33E+05 1,06E+06 4,63E+08 4,21E-07 6,901E-08 4,644E-06 P10 3,34E+06 1,58E+05 3,45E+09 9,38E-05 3,33E-03 1,54E-03 P16 7,14E+02 5,01E+04 5,55E+08 1,73E-07 6,81E-05 9,33E-04 P19 4,65E+02 0,00E+00 2,52E+02 2,31E-04 1,78E-02 0,00E+00 P30 7,55E+04 3,95E+03 2,68E+08 8,29E-05 5,59E-06 3,42E-04 P33 1,61E+04 1,33E+03 2,34E+07 2,70E-08 1,47E-09 4,25E-07 P34 9,24E+00 5,43E+04 1,27E+01 3,01E-06 1,02E-04 6,77E-08 P35 7,61E+09 4,92E+06 8,59E+09 1,61E-03 1,22E-03 4,23E-05 P36 4,76E+04 0,00E+00 0,00E+00 2,69E-04 1,86E-02 1,65E-05 P37 7,70E+03 0,00E+00 0,00E+00 7,20E-05 1,35E-08 2,60E-05 P38 2,15E-07 0,00E+00 0,00E+00 1,85E-07 2,21E-04 3,36E-02 P39 1,66E+03 6,84E+05 4,34E+09 4,73E-08 7,83E-06 1,50E-04 P40 1,09E-04 5,29E-05 1,29E-04 6,44E-09 7,56E-10 3,75E-09 P41 1,23E-05 4,00E-09 6,83E-03 2,23E-10 6,13E-13 7,03E-10 P42 5,43E-05 1,10E-03 0,00E+00 9,67E-08 4,89E-07 5,23E-09 P43 1,17E-02 0,00E+00 0,00E+00 8,69E-06 6,76E-06 9,44E-07 P44 1,08E-04 0,00E+00 0,00E+00 9,13E-08 5,93E-07 1,26E-06 Cava 1,12E+09 7,92E+08 9,99E+08 3,95E-05 4,68E-04 3,36E-05 BNF 6,94E+11 1,34E+12 7,01E+11 3,48E-03 7,51E-03 1,37E-03 onsulta 0,00E+00 0,00E+00 0,00E+00 4,912E-06 0,0353742 8,093E-06 More the water is oxidizing the ratio of U +6 / U +4 is higher higher mobility of uranium in the solution.

Main chemical species - PHREEQC

Main chemical species - PHREEQC

5 - Hidrogeochemistry Conceptual Model

Schematic geological section Minerals Wells profile

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