Modeling the DR-A in-situ diffusion experiment (Opalinus Clay): Ionic strength effects on solute...
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Modeling the DR-A in-situ diffusion experiment (Opalinus Clay):
Ionic strength effects on solute transport
Josep M. Soler (IDAEA-CSIC, Catalonia, Spain)
Carl I. Steefel (LBNL, USA)
Olivier X. Leupin (NAGRA, Switzerland)
Thomas Gimmi (PSI & Univ. Bern, Switzerland)
Mont Terri ProjectDisturbances, diffusion and retention (DR-A)
Nagra, Switzerland
NWMO, Canada
DOE, USA
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In-situ diffusion experiments, Mont Terri URL (15 years)
• DI: HTO, I-
• DI-A: HTO, I-, 22Na+, Cs+ DI-B: 2H, I-, 6Li+, 87Rb+
• DI-A2: HTO, I-, Br-, 85Sr2+, Cs+, 60Co2+, Eu3+
• DR: 2H, 18O, 133Ba2+, 60Co2+, 137Cs+, Eu3+, 152Eu3+
HTO, Br-, I-, SeO42-, 22Na+, 85Sr2+, Cs+
injection line
re-circulation line
tracer injection vial
flow meter
Nitrogen
balance
overpressurevalve
manometer
sampling port
detector
data acquisition for-detection
3 m
5 m
8 m
9 m
PVC liner
steel linerdiam. 350 mm
packer
Screen(Teflon)
central tube PFA coated
76 mm
circulation pump
plexi glasscabinet
Packer system control unit
electric cooler
injection lineinjection line
re-circulation line
tracer injection vial
flow meter
Nitrogen
balance
overpressurevalve
manometer
sampling port
detector
data acquisition for-detection
3 m
5 m
8 m
9 m
PVC liner
steel linerdiam. 350 mm
packer
Screen(Teflon)
central tube PFA coated
76 mm
circulation pump
plexi glasscabinet
Packer system control unit
electric cooler
Proven experimental setup
Circulation of synthetic solution at equilibrium with rock (OPA)+ tracers
Data: (1) monitoring (2) rock profiles
Successful for conservativeand moderately-sorbing tracers
Anion exclusionSorption of cations(Effect of filters)(BDZ)
1 m
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DR-A: Objectives
• Induce a perturbation in the system
• Check the capabilities of reactive transport codes
DR-A: Concept
(1) Conventional in-situ diffusion experiment (189 days) Synthetic OPA pw + tracers
HTO, I-, Br-, Cs+, 85Sr2+, 60Co2+, Eu3+
(2) Replace synthetic OPA pw with high-salinity solution 0.5 M NaCl + 0.56 M KCl 85Sr2+
Modeling by different teams:PSI, Univ. Bern (T. Gimmi), Univ. British Columbia (U. Mayer, M. Xie),Lawrence Berkeley Natl. Lab. (C. Steefel), IDAEA-CSIC, T. Appelo
Nov. 2011 – Nov. 2013
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Basis: Modeling with CrunchFlow, 1D – radial
• r = 4.16 cm (circle with same perimeter as ellipse)• Excess volume of ca. 1%. Borehole capacity decreased by the same factor for same volume as ellipse.
Diffusion domain(bedding plane)
x
y
BoreholeDip = 32.5o
1D
cDtc
etot
c = concentration in solution [mol.m-3]
t = time [s]
De = effective diffusion coefficient [m2.s-1]
ctot = total concentration of tracer [mol.m-3]
scc dtot
f = diffusion accessible porosity
rd = bulk dry density [kg.m-3]
s = sorbed tracer conc. [mol.kg-1]
sd )1( 3/2700 mkgs
filter
gap
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Modeling with CrunchFlowMC, 1D – radial
All chemical species modeled simultaneouslyNo decay in the model (decay-corrected data)
(1) Dynamic calculation of bulk porosity and microporosity (EDL)
Microporosity
Aclay (m2/m3rock), lDL: n. of Debye lenghts
Total porosity (fixed) = bulk porosity + microporosity
IADA DL
DLclayLDLclayEDL
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(2) Concentrations in EDL related to concs. in bulk water through the meanelectrical potential of the diffuse layer ( )
Mean electrical potential calculated from charge balance between surface chargeand diffuse layer.
Tkez
CCB
miBi
EDLi
exp
m
Micropor. (EDL), CiEDL
Micropor. (EDL), CiEDL
Bulk porosity, CiB
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Micropor. (EDL), CiEDL
Micropor. (EDL), CiEDL
Bulk porosity, CiB BBB
e DD 0
EDLEDLEDLe DD 0
EDLEDLEDLe DD 0
t = 1 in the rockD0 = Dp
(3) Different De values in the microporosity (EDL) and bulk porosity.
iiei
iiei CDRTFz
CDJ ,, Nernst-Planck equation
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run 17b
PARAMETERS
Borehole: well mixed, De = 1e-4 m2/s, a = 3.262(tank, lines, inner gap: 10243 mL; Gimmi, 2003, PSI AN 44-13-03)
Filter: well mixed, De = 1e-5 m2/s, f = 0.445
Gap: De = 2e-9 m2/s, f = 0.989
Rock: total porosity f = 0.15
Bulk porosity Cations, HTO: Dp = 1e-9 m2/s Anions: Dp = 3e-10 m2/s
Microporosity (EDL) Cations, HTO: Dp = 9e-11 m2/s (except Cs+, Dp = 1e-9 m2/s) Anions: Dp = 2e-11 m2/s lDL = 6 Surf. charge on illite: 0.2 eq/kg (B&B, 2000) (25 vol%, 200 m2/g)
Sorption of K had to be decreased (logK(PS-K)=-0.4 instead of -1.1)
Calculation up to 729 days (final 6-day back-diffusion not included)
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INITIAL SOLUTION COMPOSITIONSTotal concentrations in mol/kg_H2O
Rock/filter/gap Borehole (1) Borehole (2)
T (°C) 18 18 18
pH 7.6 7.6 7.6
Na+ 2.59×10-1 2.59×10-1 5.00×10-1
K+ 1.64×10-3 1.64×10-3 5.60×10-1
Mg2+ 1.80×10-2 1.80×10-2 1.47×10-2
Ca2+ 1.88×10-2 1.88×10-2 2.30×10-2
Sr2+ 5.10×10-4 5.10×10-4 4.54×10-4
Cl- 3.00×10-1 3.00×10-1 1.12×100 charge
SO42- 1.37×10-2 1.37×10-2 2.37×10-4
HCO3- 7.25×10-3 charge 8.19×10-3 charge 5.63×10-4 PCO2,atm
Cs+ 2.00×10-8 2.069×10-4 6.23×10-6
SiO2(aq) 6.71×10-5 quartz 6.71×10-5 quartz 5.76×10-5 quartz
Al3+ 1.18×10-8 illite 1.18×10-8 illite 2.88×10-9 illite
I- 1.00×10-12 1.09×10-2 8.60×10-3
Br- 7.15×10-4 1.09×10-2 8.86×10-3
40 species in solution
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CATION EXCHANGE – Opalinus Clay(Bradbury & Baeyens, 2000; Jakob et al., 2009;Van Loon et al., 2009)
log KSite capacity (eq/kg)
FES-Cs + Na+ = FES-Na + Cs+ -7-01.05×10-4
FES-K + Na+ = FES-Na + K+ -2.4
II-Cs + Na+ = II-Na + Cs+ -3.28.4×10-3
II-K + Na+ = II-Na + K+ -2.1
PS-Cs + Na+ = PS-Na + Cs+ -1.6
9.5×10-2
PS-K + Na+ = PS-Na + K+ -0.4 (-1.1)
PS2-Ca + 2 Na+ = 2 PS-Na + Ca2+ -0.67
PS2-Mg + 2 Na+ = 2 PS-Na + Mg2+ -0.59
PS2-Sr + 2 Na+ = 2 PS-Na + Sr2+ -0.59
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RESULTSBorehole
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0.3
0.4
0.5
0.6
0.7
0.8
0.9
1.0
1.1
0 100 200 300 400 500 600 700
C/C
0
t (d)
HTO model
HTO data
I model
I data
Br model
Br data
HTO, I-, Br-
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0.0
0.2
0.4
0.6
0.8
1.0
0 100 200 300 400 500 600 700
C/C
0
t (d)
Cs+
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0.0E+00
1.0E-01
2.0E-01
3.0E-01
4.0E-01
5.0E-01
6.0E-01
0 100 200 300 400 500 600 700
K (
mo
l/L
)
t (d)
0.0E+00
1.0E-01
2.0E-01
3.0E-01
4.0E-01
5.0E-01
6.0E-01
0 100 200 300 400 500 600 700
Na
(m
ol/
L)
t (d)
0.0E+00
1.0E-02
2.0E-02
3.0E-02
4.0E-02
5.0E-02
0 100 200 300 400 500 600 700
Mg
(m
ol/
L)
t (d)
0.0E+00
1.0E-02
2.0E-02
3.0E-02
4.0E-02
5.0E-02
6.0E-02
0 100 200 300 400 500 600 700
Ca
(m
ol/
L)
t (d)
Ca2+ Mg2+
Na+ K+
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0.0E+00
2.0E-03
4.0E-03
6.0E-03
8.0E-03
1.0E-02
1.2E-02
1.4E-02
1.6E-02
0 100 200 300 400 500 600 700
SO
4 (
mo
l/L
)
t (d)
0.0E+00
2.0E-01
4.0E-01
6.0E-01
8.0E-01
1.0E+00
1.2E+00
1.4E+00
0 100 200 300 400 500 600 700
Cl
(mo
l/L
)
t (d)
0.0E+00
3.0E-04
6.0E-04
9.0E-04
1.2E-03
1.5E-03
1.8E-03
0 100 200 300 400 500 600 700
Sr
(mo
l/L
)
t (d)
Sr2+
Cl-SO4
2-
?
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RESULTSRock
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0.0
2.0
4.0
6.0
8.0
10.0
12.0
14.0
0.0 10.0 20.0 30.0 40.0
Poro
sity
(%)
d (cm)
Bulk por.
Micropor.
Model porosities, t = 729 d(total por. = 15%, fixed)
EDL
Bulk
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0.0E+00
1.0E-03
2.0E-03
3.0E-03
4.0E-03
5.0E-03
6.0E-03
7.0E-03
0 5 10 15 20
I (m
ol/L
)
d (cm)
11.60
11.80
11.85
Model-b
Model-mp
0.0
5.0
10.0
15.0
20.0
25.0
30.0
35.0
40.0
45.0
50.0
0 5 10 15 20
H-3
(Bq/
g_pw
)d (cm)
11.60
11.80
11.85
Model-b
Model-mp
I-
Aqueous extract data (PSI)
HTO
Back-diffusion signal(final 6 days)
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1.0E-03
2.0E-03
3.0E-03
4.0E-03
5.0E-03
6.0E-03
7.0E-03
0 5 10 15 20
Br (m
ol/L
)
d (cm)
11.60
11.80
Model-b
Model-mp
2.0E-01
3.0E-01
4.0E-01
5.0E-01
6.0E-01
7.0E-01
8.0E-01
0 5 10 15 20
Cl (m
ol/L
)d (cm)
11.60
11.80
Model-b
Model-mp
Aqueous extract data(U. Bern)
Cl-
Br-
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0
10
20
30
40
50
60
70
80
0 5 10 15 20
C (m
eq/k
g)
d (cm)
Ca
K
Mg
Na
Sr
Ca model
K model
Mg model
Na-model
Sr model
Ni-en extract data (U. Bern) – exchange complex
Prof. 11.60
Prof. 11.80
0
10
20
30
40
50
60
70
80
0 5 10 15 20
C (m
eq/k
g)
d (cm)
Ca
K
Mg
Na
Sr
Ca model
K model
Mg model
Na-model
Sr model
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BOREHOLE• Good match of borehole concentrations (some overestimation of Cs+ right after solution exchange; also problem with SO4
2-)• Clear effect of increased salinity on anions: Reduced microporosity (EDL), Dp(B) > Dp(EDL), CB > CEDL • Also effect on HTO: Dp(B) > Dp(EDL)
PROFILES – aqueous extracts• Anions, HTO: approximate match of profiles, concentrations on the low side• Cations: good match for Na+, K+; no match for Ca2+, Mg2+
PROFILES – Ni-en extracts• Good match of transport distances and composition of the exchange complex• K sorption had to be decreased (logK(PS-K)=-0.4 instead of -1.1)
Summary and conclusions
Thank you for your attention