DIFUSIN, aplicado a formaciones arcillosas

Rocas impermeables
Transporte dominado por difusin
Medio saturado
Horseman et al. (1996) Water, Gas and Solute Movement Through Argillaceous Media.
NEA-OECD Report CC-96/1. http://www.nea.fr/html/pub/webpubs/welcome.html#rwm
x
c
D J
e
c
c
=
1D
J: Flujo de soluto (mol/m
2
roca/s)
D
e
(m
2
/s): Coef. efectivo de difusin
c: Concentracin (mol/m
3
solucin)
x: distancia (m)
( )
|
.
|

\
|
c
c
c
c
=
c
c
=
c
c
x
c
D
x x
J
t
c
e
|
|: porosidad (-)
2
2
2
2
x
c
D
x
c D
t
c
p
e
c
c
=
c
c
=
c
c
|
Si | y D
e
son constantes
D
p
(m
2
/s): Coef. de difusin de poro
Para solutos que se adsorben (adsorcin lineal, K
D
)
c K s
D
=
s: Concentracin adsorbida (mol/kg_slido)
K
D
: Coeficiente de distribucin (m
3
/kg)
|
.
|

\
|
c
c
c
c
=
c
+ c
x
c
D
x t
c K c
e
D d
) ( |

d
: Densidad seca (kg_slido/m
3
_roca)
Si |,
d
, K
D
y D
e
son constantes:
2
2
x
c
D
t
c
e
c
c
=
c
c
o
2
2
2
2
x
c
D
x
c D
t
c
a
e
c
c
=
c
c
=
c
c
o
|

| | o
D d
D d
K
R
R K
+ =
= + =
1
D
a
(m
2
/s): Coef de difusin aparente
o: Factor de capacidad (-)
R: Factor de retardo (-)
POROSIDAD

Pearson F. J. (1999) What is the porosity of a mudrock? In: Muds and Mudstones: Physical
and Fluid Flow Properties. Geological Society, London, Special Publications 158, 9-21.
Porosidad fsica o total |
tot
: Incluye los poros aislados

solid
d
tot

| = = 1
roca de volumen
huecos de volumen
Porosidad conectada: Medida normalmente a partir del contenido

de agua (|
wc
)

sat sat
sat
m
m
m
m m
wc
sec sec
1 =

=
Contenido de agua
fluid solid
solid
fluid
sat
wc
wc wc
wc
wc

|
) 1 ( +
= =
tot wc
| | s

sat
: Dens. saturada (kg_slido+fluido/m
3
_roca)
Porosidad accesible para adveccin |
adv
: No incluye poros aislados

o sin salida.

v
v
D
i
adv
= |
v
D
: Velocidad Darcy (m
3
fluido/m
2
roca/s)
v: Velocidad lineal del fluido (m/s)
tot wc
i
adv
| | | s s
En la literatura se usa tambin el trmino porosidad efectiva
Porosidad accesible para difusin |
dif
2
2
2
2
x
c
D
x
c D
t
c
i
i
p
i
i
dif
i
e i
c
c
=
c
c
=
c
c
|
2
2
2
2
x
c
D
x
c D
t
c
i
i
a
i
i
i
e i
c
c
=
c
c
=
c
c
o
i
dif
i
D d
i
i
i
dif
i
D d
i
dif i
K
R
R K
|

| | o
+ =
= + =
1
Conservativo
No conservativo
+
+
Charge (+)
EXCLUSIN ANINICA
0
+
+
+
+
+ +
+
+
+
+
+ +
+
+
+
clay
clay
tot wc
O H
dif
O H
adv
| | | | s ~ <
2 2
tot wc
i
dif
i
adv
| | | | s s <
Arcillas compactas:
sedimentation of clay platelets resulting
in a house-of-cards structure
compaction by overburden load leading to
preferential orientation of clay platelets
: clay platelet
pressure
d
i
r
e
c
t
i
o
n

o
f

s
e
d
i
m
e
n
t
a
t
i
o
n
+ +
ANISOTROPA: D
e
(||) > D
e
()
- - - - - -
- - - - - -
- - - - - -
- - - - - -
- - - - - -
- - - - - -
- - - - - -
- - - - - -
- - - - - -
- - - - - -
- - - - - -
- - - - - -
- - - - - -
- - - - - -
- - - - - -
- - - - - -
- - - - - -
- - - - - -
- - - - - -
- - - - - -
- - - - - -
- - - - - -
- - - - - -
- - - - - -
- - - - - -
- - - - - -
- - - - - -
- - - - - -
- - - - - -
- - - - - -
- - - - - -
- - - - - -
- - - - - -
- - - - - -
- - - - - -
- - - - - -
- - - - - -
- - - - - -
- - - - - -
- - - - - -
diffusion in OPA is anisotropic

rock capacity (porosity) in
OPA is isotropic

0
1 10
-11
2 10
-11
3 10
-11
4 10
-11
5 10
-11
6 10
-11
7 10
-11
8 10
-11
0 2 10
-11
4 10
-11
6 10
-11
8 10
-11
HTO (BE)
Cl-36 (BE)
Na-22 (BE)
HTO (MT)
Cl-36 (MT)
Na-22 (MT)
D
e

(
p
a
r
a
l
l
e
l
)


[
m
2

s
-
1
]
D
e
(perpendicular) [m
2
s
-1
]


D
e
(par)
D
e
(per)
= 4.2 6.2
0
0.2
0.4
0.6
0.8
1
0 0.2 0.4 0.6 0.8 1
HTO (BE)
Cl-36 (BE)
Na-22 (BE)
HTO (MT)
Cl-36 (MT)
Na-22 (MT)
r
o
c
k

c
a
p
a
c
i
t
y


(
p
a
r
a
l
l
e
l
)
rock capacity (perpendicular)
Anisotropa - Opalinus Clay
EXPERIMENTO THROUGH-DIFFUSION

Se utiliza para medir el coef. efectivo de difusin D
e
y la
porosidad accesible |
dif
para especies conservativas o que se
adsorban slo dbilmente.
x=0 x=L
C(0,t)=C
0
C(L,t)=0

J
Reservorio 1 Reservorio 2 Muestra
Van Loon L. R., Soler J. M. y Bradbury M. H. (2003) Diffusion of HTO,
36
Cl
-
and
125
I
-
in Opalinus
Clay samples from Mont Terri. Effect of confining pressure. Jour. Cont. Hydrol. 61, 73-83.
Diseo experimental
Resultados
A
c
t
i
v
i
d
a
d

(
B
q
)

o

N

m
.

d
e

m
o
l
e
s

o

G
r
a
m
o
s

B
q
/
m
2
/
s

o

m
o
l
/
m
2
/
s

o

g
/
m
2
/
s

Solucin analtica
Jakob et al. (1999) Diffusion and Sorption on Hardened Cement Pastes Experiments
and Modelling Results. PSI Bericht Nr. 99-05 (p.94-97, 188-189).
http://les.web.psi.ch/publications/Liste99.html
2
2
x
c
D
t
c
a
c
c
=
c
c
L x
e
x
c
D t L J
=
c
c
= ) , (
Se resuelve
combinado con
x=0 x=L
C(0,t)=C
0
C(L,t)=0

J
Reservorio 1 Reservorio 2 Muestra
0 ) , (
) , 0 (
0 ) 0 , (
0
= =
= =
= =
t L x c
c t x c
t x c
( )
|
|
.
|

\
|
)
`

=1
2
2 2
2 2 2
0
exp
1 2
6
) , (
n
e
n
e
low
L
t n D
n L
t D
V
c L S
t L c
o
t
t
o o
( )
|
|
.
|

\
|
)
`

=1
2
2 2
2 2 2
0
exp
1 2
6
) , (
n
e
n
e
moles
L
t n D
n L
t D
c L S t L n
o
t
t
o o
6
) , (
0
2
0
o

|
|
.
|

\
|


=
low
e
low
V
c L S
t
L
D
V
c L S
t L c
6
) , (
0
2
0
o

|
.
|

\
|
= c L S t
L
D
c L S t L n
e
moles
Solucin
Estado estacionario (t)
S: Seccin transversal de la muestra (m
2
)
V
low
: Volumen del reservorio de salida (m
3
)
Estado estacionario

La pendiente de la asntota es proporcional a D
e
El corte con el eje de ordenadas (t=0) es proporcional al factor
de capacidad o (porosidad | para especies conservativas)
Opalinus Clay
Benken
TERTIR
MALM
DOGGER
LIAS
KEUPER
MUSCHELKALK
0
200
400
600
800
1000
OPA
T
i
e
f
e


(
M
e
t
e
r

u
.

T
e
r
r
a
i
n
)
Mont Terri
EXPERIMENTO EN CAMPO
Opalinus Clay:
- Laboratorio subterrneo de Mont Terri (1) -
Opalinus Clay:
- Laboratorio Subterrneo de Mont Terri (2) -
DI-Niche
Mineral Weight percent
Calcite 17 11
Dolomite/ankerite 0.6 0.5
Siderite 5 3
Quartz 20 5
Feldspar 3 1
Pyrite 0.8 0.4
C
org
0.6 0.2
Phyllosilicates
- illite
- illite/smectite
- kaolinite
- chlorite
53 11
18 6
14 4
17 6
5 2
Composicin de
Opalinus Clay
Chemical-Physical properties
Density (bulk, sat.): 2500 kg
.
m
-3

Porosity: 0.15
Pore water: NaCl 0.2 - 0.4 M
CEC: 100 meq
.
kg
-1

pH: 7 - 8
E
h
: -140 mV to -240 mV (SHE)
Experimento in situ: diseo experimental
N
2
hydraulic packer
pump
flowmeter
manometer
pressure
transducer
packer inflation line
sintered stainless steel screen
scale
tracer
data
acquisition
sampling
bypass
1 m
3 m
pressure vessel
DI-A
Experimento in situ: perfiles de trazadores
Diffusion
bedding plane
bore hole
tracer cocktail
sintered steel filter
0
20
40
60
80
100
120
0 2 4 6 8 10 12
a
c
t
i
v
i
t
y


[
B
q
/
g
]
distance from borehole [cm]
Concentration profile
overcoring
Drilling of BDI-A1 Surface equipment
Experimental
site
Packer removal
Overcoring
Drillcore documentation
Subcoring, sampling
Experimento in situ: Modelo de diferencias finitas
2D. Concepto: Difusin a lo largo de los planos de
estratificacin
( ) c D
t
c
e
tot
V V =
c
c
c = concentration in solution [mol
.
m
-3
]
t = time [s]
D
e
= effective diffusion coefficient [m
2
.
s
-1
]
c
tot
= total concentration of tracer

s c c
d tot
| + =
| = diffusion accessible porosity

d
= bulk dry density [kg
.
m
-3
]
s

= sorbed tracer conc. [mol
.
kg
-1
]

x
y
c
init
=c
0
Diffusion domain
(bedding plane)
c
tot,init
=c
back
El ajuste simultneo de (a) los perfiles y (b) la evolucin del trazador
en el circuito de inyeccin proporciona un valor nico de (De, o)

Resultados exp. in situ: HTO s=0 (sin adsorcin)

Field study: D
e
= 5.4 x 10
-11
m
2
.
s
-1

o = 0.18 (porosity)
Lab. study: D
e
= 5.4 x 10
-11
m
2
.
s
-1

o = 0.17 (porosity)
Resultados exp. in situ: I
-
s=0 (sin adsorcin)
Field study: D
e
= 1.3 x 10
-11
m
2
.
s
-1

o = 0.09 (porosity)
Lab. study: D
e
= 1.6 x 10
-11
m
2
.
s
-1

o = 0.08 (porosity)
full water
content
0.56 x water content
Field study: D
e
= 7.2 x 10
-11
m
2
.
s
-1

o = 0.62 (o = | +
d
K
d
)
Lab. study: D
e
= 7.2 x 10
-11
m
2
.
s
-1

o = 0.62 (o = | +
d
K
d
)
Resultados exp. in situ:
22
Na
+
s=K
d
c
(adsorcin lineal)
Resultados exp. in situ: Cs
+
s = a c
b
(adsorcin no lineal)
Field study: D
e
= 3.0 x 10
-10
m
2
.
s
-1

s = 0.186
.
c
0.53

Lab. study: ---------------------
s = 0.372
.
c
0.53

Resultados del exp. in situ: D
e
(||), o
Resumen
Muy buena correspondencia entre laboratorio y campo

Lab. Studies DI DI-A
Tracer
D
e
[m
2
.
s
-1
]
o
D
e
[m
2
.
s
-1
]
o
D
e
[m
2
.
s
-1
]
o
HTO 5.4x10
-11
0.17 5.0x10
-11
0.15 5.4x10
-11
0.18
I
-
(
36
Cl
-
) 1.6x10
-11
0.08 1.5x10
-11
0.13 1.3x10
-11
0.09
22
Na
+
7.2x10
-11
0.62 - - 7.2x10
-11
0.62
Cs
+
- s=0.372c
0.53
- - 3.0x10
-10
s=0.186c
0.53


ANLOGO NATURAL: MONT TERRI
Rbel et al. (2002) Geochim. Cosmochim. Acta 66, 1311-1321.
Distribucin de
4
He a travs de la formacin ( a la estratificacin)
Se asume estado estacionario entre su formacin radiognica
y su transporte por difusin fuera de la formacin
0
2
2
0
2
2
2
) (
tnel] - m [932 0
tnel] - m [743 ) 0 (
0
c
D
Lx A
D
x A
x c
x
c
c x c
A
x
c
D
t
c
a
is
a
is
L
x
is a
+ + =
=
c
c
= =
= +
c
c
=
c
c
=
D
a
= 3.51.3 x 10
-11
m
2
/s
Aplicacin del valor obtenido de D
a
a la composicin isotpica
del agua (o
18
O, oD) en la formacin
oo
o
0 ) 0 , (
oo
o
-70 ) , 0 (
0
1
2
2
= = =
= = =
c
c
=
c
c
c t x c
c L x c
x
c
D
t
c
a
Modelo 1D para oD
( )
( ) ( ) ( )
|
|
.
|

\
|
(

)
`

+
)
`

+
+

+ =

=0
2
2
2
0 1 0
2
1 2
cos
4
1 2
exp
1 2
1 4
1
) , (
n
a
n
L
x n
L
t n D
n
c c c t x c
t t
t
Anlogo natural (Mont Terri, H
2
O, escala 10
+2
m)

D
a
= 3.51.3 x 10
-11
m
2
/s
|
wc
= 0.12 0.19

D
e
= | D
a
= 2.6 9.1 x 10
-12
m
2
/s

Experimentos through-diffusion (HTO, , escala 10
-2
m)

D
e
= 1.4 0.1 x 10
-11
m
2
/s