Presentation to CNSC and NRCan: Diffusion Measurements CNSC, Ottawa, April 19, 2010 Outline . Methods . Gravimetric water loss porosity . Radiography • Iodide accessible porosity • De - iodide . Through diffusion • Iodide and HTO accessible porosity • De – iodide/HTO . Results . Porosity . De values • Variability vs depth • Differences between tracers • Anisotropy • International comparison Methods: Water Loss Porosity 92.38 92.37 DGR2_677.11 (4 Bottom) 92.36 92.35 M(sat) = 92.322 g 92.34 92.33 M(sat) (g) M(sat) Msat Msub 92.32 Vrock ρbrine 92.31 92.3 Msat Mdry 0 5 10 15 20 Vvoids Time (min) (1 x) ρbrine Vvoids Msat Mdry w 100% 100% Vrock (1 x)(Msat Msub ) Methods: Radiography SAMPLE PREPARATION . Mini cores 20 mm drill core w PB NB 20 mm 20 slice 11 mm 65 mm Methods: Radiography x-RAY ABSORPTION . Beer-Lambert law: I I0 exp μd d f (density, I0 I Source atomic number) µ . Porous medium: μ 1 μm μp SOLID MATRIX PORES Methods: Radiography Iodide-accessible porosity and diffusion coefficient Results: Porosity Porosity 0.00 0.02 0.04 0.06 0.08 0.10 0.12 0.14 0.16 0.18 0.20 150 200 Salina E-G 250 Salina B,C 300 Salina A0-2 350 Goat Island 400 Cabot Head 450 ) m ( Queenston h t 500 p e D 550 Georgian Bay 600 Blue Mountain 650 Cobourg 700 Sherman Fall Kirkfield 750 Water-loss NaI RAD Coboconk 800 NaI TD Gull River HTO TD NB: open symbols 850 PB: closed symbols Results: De Method Comparison 1 x 10-9 Radiography Through-diffusion Q78NB UNB P. Vilks AECL Q84NB Q89NB ) shale shale Q105NB -1 1 x 10-10 Q87PB ·s 2 Q96PB (m Q105PB p C36NB D 1 x 10-11 C44NB limestone limestone C56NB C36PB C44PB Mean 1 x 10-12 2 Results: De (m /s) 2 De (m /s) 1.0E-14 1.0E-13 1.0E-12 1.0E-11 1.0E-10 150 DGR2 NaI DGR3 NaI 200 Salina E-G DGR4 NaI DGR2 HTO 250 DGR3 HTO DGR4 HTO Salina B,C 300 Salina A0-2 350 Goat Island 400 Cabot Head 450 ) m ( Queenston h t 500 p e D 550 Georgian Bay 600 Blue Mountain 650 Cobourg 700 Sherman Fall Kirkfield 750 Coboconk PSI - Switzerland 800 Gull River NB: open symbols PB: closed symbols 850 Results: Anion Exclusion 0.18 0.18 a) RAD Shale b) TD Shale NaI Dolostone NaI 0.16 Siltstone 0.16 Hardbed limestone NaI 1:1 Arg. Limestone NaI HTO Dolostone HTO 1:1 I I 0.14 0.14 Shale HTO Arg. Limestone or or or or Hardbed limestone HTO I I 0.12 0.12 Arg. Limestone HTO 0.10 0.10 1:2 1:2 0.08 0.08 0.06 0.06 Tracer-accessibleporosity, Tracer-accessibleporosity, 0.04 0.04 Tracer-accessibleTracer-accessibleporosity,porosity, 0.02 0.02 0.00 0.00 0.00 0.02 0.04 0.06 0.08 0.10 0.12 0.14 0.16 0.18 0.00 0.02 0.04 0.06 0.08 0.10 0.12 0.14 0.16 0.18 Water-loss porosity, w Water-loss porosity, w Results: Anion Exclusion 1.E-11 TD ) = 3:1 1:1 (NaI e (HTO):D D e 1.E-12 /s), HTOHTO /s), /s), 2 2 (m (m e e D D 1.E-13 Shale Hardbed limestone Arg. Limestone 1.E-14 1.E-14 1.E-13 1.E-12 1.E-11 2 De (m /s), NaI Results: Anisotropy 1.E-10 ) = 7:1 1:1 (NB e (PB):D D e 1.E-11 /s), PBPB /s), /s), 2 2 1.E-12 (m (m e e D D 1.E-13 Shale NaI Siltstone NaI Dolostone NaI Arg. Limestone NaI Arg. Limestone HTO 1.E-14 1.E-14 1.E-13 1.E-12 1.E-11 1.E-10 2 De (m /s), NB Results: International Comparison 1.0 0.25 Water 1.0 International data limestones Water 0.9 International data siltstones 0.8 3.0 2.5 2.0 1.5 International data clays/shales 0.6 0.8 MB Ordovician limestone 0.20 0.4 MB Ordovician shale 0.7 1.5 0.2 2.0 0.0 0.6 2.5 0.15 1.0E-14 1.0E-12 1.0E-10 1.0E-08 3.0 0.5 0.4 0.10 accessible accessible porosity accessible accessible porosity - - International data limestones 0.3 International data clays/shales Anion Water MB Ordovician limestone 0.2 0.05 MB Ordovician shale MB Silurian dolostone 0.1 MB Silurian siltstone MB Silurian shale 0.0 0.00 1.0E-14 1.0E-13 1.0E-12 1.0E-11 1.0E-10 1.0E-09 1.0E-08 1.0E-14 1.0E-13 1.0E-12 1.0E-11 1.0E-10 1.0E-09 1.0E-08 De-HTO (m2/s) De-Cl-,I- (m2/s) m De D0 Summary -14 -11 2 . De values range from 10 to 10 m /s; >99% of data are lower than 10-11 . Anion exclusion is evident in the data such that I ≈ 0.5 HTO . Anisotropy ratios (DePB:DeNB) range from 1 to 7 . De values are very low by international standards Discussion? Definitions L 2 Tortuosity: e L Tortuosity factor: f Pore water diffusion coefficient: Dp f D0 Effective diffusion coefficient: De w f D0 De Apparent diffusion coefficient: Da Rock capacity factor: d K d w = water-loss porosity; d = diffusion-accessible porosity; = constrictivity Presentation to CNSC and NRCan: Diffusion Measurements CNSC, Ottawa, April 19, 2010 Outline . Methods . Gravimetric water loss porosity . Radiography • Iodide accessible porosity • De - iodide . Through diffusion • Iodide and HTO accessible porosity • De – iodide/HTO . Results . Porosity . De values • Variability vs depth • Differences between tracers • Anisotropy • International comparison Methods: Water Loss Porosity 92.38 92.37 DGR2_677.11 (4 Bottom) 92.36 92.35 M(sat) = 92.322 g 92.34 92.33 M(sat) (g) M(sat) Msat Msub 92.32 Vrock ρbrine 92.31 92.3 Msat Mdry 0 5 10 15 20 Vvoids Time (min) (1 x) ρbrine Vvoids Msat Mdry w 100% 100% Vrock (1 x)(Msat Msub ) Methods: Radiography SAMPLE PREPARATION . Mini cores 20 mm drill core w PB NB 20 mm 20 slice 11 mm 65 mm Methods: Radiography x-RAY ABSORPTION . Beer-Lambert law: I I0 exp μd d f (density, I0 I Source atomic number) µ . Porous medium: μ 1 μm μp SOLID MATRIX PORES Methods: Radiography Iodide-accessible porosity and diffusion coefficient Results: Porosity Porosity 0.00 0.02 0.04 0.06 0.08 0.10 0.12 0.14 0.16 0.18 0.20 150 200 Salina E-G 250 Salina B,C 300 Salina A0-2 350 Goat Island 400 Cabot Head 450 ) m ( Queenston h t 500 p e D 550 Georgian Bay 600 Blue Mountain 650 Cobourg 700 Sherman Fall Kirkfield 750 Water-loss NaI RAD Coboconk 800 NaI TD Gull River HTO TD NB: open symbols 850 PB: closed symbols Results: De Method Comparison 1 x 10-9 Radiography Through-diffusion Q78NB UNB P. Vilks AECL Q84NB Q89NB ) shale shale Q105NB -1 1 x 10-10 Q87PB ·s 2 Q96PB (m Q105PB p C36NB D 1 x 10-11 C44NB limestone limestone C56NB C36PB C44PB Mean 1 x 10-12 2 Results: De (m /s) 2 De (m /s) 1.0E-14 1.0E-13 1.0E-12 1.0E-11 1.0E-10 150 DGR2 NaI DGR3 NaI 200 Salina E-G DGR4 NaI DGR2 HTO 250 DGR3 HTO DGR4 HTO Salina B,C 300 Salina A0-2 350 Goat Island 400 Cabot Head 450 ) m ( Queenston h t 500 p e D 550 Georgian Bay 600 Blue Mountain 650 Cobourg 700 Sherman Fall Kirkfield 750 Coboconk PSI - Switzerland 800 Gull River NB: open symbols PB: closed symbols 850 Results: Anion Exclusion 0.18 0.18 a) RAD Shale b) TD Shale NaI Dolostone NaI 0.16 Siltstone 0.16 Hardbed limestone NaI 1:1 Arg. Limestone NaI HTO Dolostone HTO 1:1 I I 0.14 0.14 Shale HTO Arg. Limestone or or or or Hardbed limestone HTO I I 0.12 0.12 Arg. Limestone HTO 0.10 0.10 1:2 1:2 0.08 0.08 0.06 0.06 Tracer-accessibleporosity, Tracer-accessibleporosity, 0.04 0.04 Tracer-accessibleTracer-accessibleporosity,porosity, 0.02 0.02 0.00 0.00 0.00 0.02 0.04 0.06 0.08 0.10 0.12 0.14 0.16 0.18 0.00 0.02 0.04 0.06 0.08 0.10 0.12 0.14 0.16 0.18 Water-loss porosity, w Water-loss porosity, w Results: Anion Exclusion 1.E-11 TD ) = 3:1 1:1 (NaI e (HTO):D D e 1.E-12 /s), HTOHTO /s), /s), 2 2 (m (m e e D D 1.E-13 Shale Hardbed limestone Arg. Limestone 1.E-14 1.E-14 1.E-13 1.E-12 1.E-11 2 De (m /s), NaI Results: Anisotropy 1.E-10 ) = 7:1 1:1 (NB e (PB):D D e 1.E-11 /s), PBPB /s), /s), 2 2 1.E-12 (m (m e e D D 1.E-13 Shale NaI Siltstone NaI Dolostone NaI Arg. Limestone NaI Arg. Limestone HTO 1.E-14 1.E-14 1.E-13 1.E-12 1.E-11 1.E-10 2 De (m /s), NB Results: International Comparison 1.0 0.25 Water 1.0 International data limestones Water 0.9 International data siltstones 0.8 3.0 2.5 2.0 1.5 International data clays/shales 0.6 0.8 MB Ordovician limestone 0.20 0.4 MB Ordovician shale 0.7 1.5 0.2 2.0 0.0 0.6 2.5 0.15 1.0E-14 1.0E-12 1.0E-10 1.0E-08 3.0 0.5 0.4 0.10 accessible accessible porosity accessible accessible porosity - - International data limestones 0.3 International data clays/shales Anion Water MB Ordovician limestone 0.2 0.05 MB Ordovician shale MB Silurian dolostone 0.1 MB Silurian siltstone MB Silurian shale 0.0 0.00 1.0E-14 1.0E-13 1.0E-12 1.0E-11 1.0E-10 1.0E-09 1.0E-08 1.0E-14 1.0E-13 1.0E-12 1.0E-11 1.0E-10 1.0E-09 1.0E-08 De-HTO (m2/s) De-Cl-,I- (m2/s) m De D0 Summary -14 -11 2 .