14
Potassium F i x a t i o n i n Smectite by Wetting a n d D r y i n g 1
2
3
Dennis D. Eberl , JanŚrodoń ,and H. Roy Northrop 1
U.S. Geological Survey, Box 25046, Federal Center, Mail Stop 404, Denver, CO 80225 Institute of Geological Sciences, Polish Academy of Sciences, 31-002 Krakow, Senacka 3, Poland U.S. Geological Survey, Box 25046, Federal Center, Mail Stop 963, Denver, CO 80225
2
3
Potassium-smectites with various layer-charge densities and layer-charge locations were subjected to as many as 100 wetting and drying cycles, thereby producing randomly interstratified illite/smectite that contained illite layers stable against exchange by 0.1 Ν SrCl or 1 Ν NaCl. The percentage of illite layers formed by this process in montmorillonite was proportional to layer-charge and, based upon very limited data, their stability with respect to sub sequent exchange was inversely proportional to alpha, the angle of tetrahedral rotation. Most of the illite layers were produced during the first 20 cycles. Sodium-smectites treated in wetting and drying experi ments that contained potassium-minerals (e.g. feldspar) formed illite layers by fixing potassium released from dissolution of the potassium-minerals. The presence of NaCl, KCl, and HCl in the experimental solutions had little effect on reaction rates, but CaCl decreased and KOH increased the rate of illitization. The reaction with KOH increased layer charge, whereas, in all of the other experiments, layer charge remained constant. Oxygen isotope data confirmed the conclusion drawn from chemical data that the reaction mechanism for illite formation at high pH (chemical reaction of 2:1 layers) differed from that found at more acid pH (mechanical rearrangement of 2:1 layers around potassium). The wetting and drying process may be responsible for producing mixed-layer i l l i t e / smectite from smectite at surface temperatures, and for accelerated dissolution of sparingly soluble potassium-minerals in sediments and soils. 2
2
One method for studying reactions that occur at the mineral-water interface is to concentrate the interface by drying a clay mineral slurry. Certain reactions are promoted by this process, for example, reactions that respond to Bronsted acidity (!_, 2). Repeated 0097-6156/86/0323-0296$08.75/0 © 1986 American Chemical Society
14.
Potassium
EBERL ET AL.
wetting yield.
and
drying
Another fixation in
of
smectite
of
its
cation
of NH
also
fields the
geochemistry
of
A
of
review
the
the
following (1)
layers For
to
clay,
example,
but
as
not
heat
(9-11) with
was
show
after
cations
may
with
remain
cation energy
to
exchange
produce
an
Fourier were
of
Κ Na,
example,
analysis determined
in
K-smectite
to
to
relative (2)
smectite
0
(OH) ]
1 0
2
heat
of
is
proportional
do
that
change
is
the
layer
expansion.
charge
smectites
NH -exchange, 4
materials.
83
fix
but
Κ by that
and
than
the
factor
in
Koyumdjisky
by
direct
simple
exchange
with
neither
cations
are
layers
samples,
thereby
structure is
K-exchange
only
-0.40
in
Schultz minerals
of
equivalents
per
K-exchange
and
after
rather
than
the
reported respect fixed
of
sensitive
(18-21).
determining (23)
(15) layers
(1.0-nm)
studied,
charge,
may
smectite
interstratified
by
clay
about
layer
however,
patterns
also
produced
of
characteristics
total
important
layers CEC
collapsed
in
the
structure
smectites
less XRD
that
Yaalon
the
therefore,
1.0/1.4/1.68-nm
of
been
K-exchange
(XRD)
glycolated
The
not
in
layers
Κ
hydration
repla ced,
contracted
in
the
standard
a
investigated
sensitivity
i l l i t e to
among
and
than the
of a
and,
randomly
the
and
exchanged
has
rest
of
or
of
(16).
[charge
not
treatment,
location,
type (17).
type
types
of
to
Simple
diffraction
More on
percentage
determined
X-ray
samples
humidity
Wyoming
13).
(air-dry)
The
(22)
three
composed
work
solvent
the
of
fixed,
completely
(12,
is
some
clay
the
sites
present,
cation with
becomes
long
smectite
absorption are
the
during as
for
respect
the a
from
1.0-nm
however,
4
with energy.
derived to
smectite
with
trapping
Ca
i l l i t e - l i k e
Ca-exchange
though
NH ,
are
4
and
be
air-dry
reveals
hydration
vermiculite
4
layers
earlier
smectite
isotherms
and N H - s m e c t i t e s
treated).
found
such
catalysis,
reversible
during
though
also K,
NH
their
(ethylene-glycol confirming
by
smectite
energy,
even K,
Mg,
1.0/1.26/1.56-nm were
many
WD forms
K-exchanged
example,
and
to
to
fields
clay
collapsed
even
and
When
the
K-
of
its
waters.
exchange
mica
For
interlayering
For
(lb).
with
that
hydration
of
Both
clays,
substantial
non-exchangeable
that
part
The
acidity.
applicable
disposal,
completely
procedure) to
only
interlayers. by
to
WD c y c l e s .
similar
replaces
Bronsted
Κ
because
decreases
completely
shale)
K-Ca
300°C.
(i.e.
its
without
reversibility,
minimal
fixed
exchange
subjected
reported (Womble
similar to
the of
nutrients.
swell, is
is
fixation
plant
swelling
is
having
applied.
heating
soil to
surface
smectite
cations
(8)
complete
scientists
waste
reaction
re-expanded
enthalpies
even
of this
by
by
phenomenon
and
cycles
The
of
with
WD
reaction
reaction:
muscovite
K-saturation,
to
concerning K-fixation
of
but
Weaver of
this
increase
(3-7).
and m o d i f i e s
mechanics,
literature
exchange
weathering
of
K-exchange
the
responds
ability
concerned
ground
patterns
Simple in
respect
(CEC),
are
soil
Work
to
availability
capacity
297
used
extensively
smectite's
fertility,
Previous
by
the
that
be
that
decreases
study
may
smectite
by
an u n d e r s t a n d i n g
of
Smectite
ions
soil
and
cycles
studied
on
in
reaction 4
been
exchange
Therefore, as
type
effect
reaction
(WD)
Κ and has
Fixation
to in
charge
extent that
of
high-
subsequent low-charge
298
GEOCHEMICAL PROCESSES AT MINERAL SURFACES (3)
Wetting
and
irreversibly, respect in
to
a
Wetting smectites
that
Κ
decreased are
for
as
much as
by
fixed
without
irreversible
that
(4)
The
and
mechanism may
stable
from
space
±60°.
The
to
cation-hydration Page K-ion the
by
Baver
minimal factor
the
hydration
energy
also
in
K-fixation
experiments by
too
in
cation
the of
layers
supported
by
K-fixation ordering of
the
Previous those
WD i s
the
Present
studies to
reaction
produce
recycled
have
never
been
that to
this
discover
methods study
in
for
how XRD
greater
layers
and
by
between
structural
also
to
smectite
holes. fit
tetrahedral
a
hypothesis based
on
a
surface-
rearrangement
greater
stability
that
development
are ions
may n o t
smectite
K-smectites
the
major
these
Κ
mechanical for
the
Rb
smectite, and
in
consistent
"hexagonal"
related
energies a
and
presented
by
that
be is
that
to
holes
though
the
Κ
potassium's
to
Cs
even
(31)
of
dehydrated
However,
distortions
by
the
hypothesis
into
of
ability
"hexagonal"
determined
turbostratic
that
elevated
burial,
illite/smectite However, from
is
to
elevated The
of
showed
is that
tridimensional
structure
(32,
WD.
may
Thus,
33)•
of
than
be
smectite
occur
in
by
chemistry
formation possible
by
this
clays
and
have
sediments
that
40), for
thereby producing suggest
systematically how
mechanism. (41-43)
previously.
are
chemical
previously
investigated
as
times that
(39,
responsible
discussed
mixed-layer was
from
such
reaction
temperatures
WD was
smectite-crystal
temperatures, long
illite/smectites
studies
illite-layer
detail
(I/S)
materials
mechanism
analysis
and
mixed-layer
older
another
affect
K-ions
2:1
interaction
that
responsible
deep
temperatures.
mechanism
environment
interlayer
considered
latter
Eberl
shown
exposed
that
low
of
accompanied
have
been
at
been
determined
studies
during
not
I/S
into
have
is
into
Study
(34-38).
indicating
WD
Κ
across
size,
layers.
selectivity
initially
prevailing
required
fit
possibility
structural
by
of
The during
of
Wetting holes
unique
to 2:1
layers. and
the
vermiculites,
30)
trapping
around
density,
ionic
cation-hydration
density.
2:1
Aims
2:1
an
its
The
because
fixation
that
comfortably
(29,
a
is
(19).
layers.
of
to
has
that and
fit
holes
consideration charge
to
the
26).
28)
others
these
rotations
of
(27,
large
into
(25,
smectites
addition,
for
radius of
fixed
well
related
correct
be
layers
from
necessary
layers.
suggested
is
of
WD i s
adjacent
layer-charge
planes
are In
(24)
result
2:1
oxygen
with are
to
is
quantities
"hexagonal"
rotating
indicated smectite
K-fixation
2:1
2:1 up
several
complication
block
coordination
by
but
to
Κ with
overnight
the
Small
between
fix
with
Mg),
of
One
can
line
the
2:1
Ca,
(18).
rearrange
may K-exchange
shaking
CEC
appears
i.e.,
adjacent
smectite
having
basal
energy,
Na,
(19).
holes
appears
as
material,
K-fixation
change
between
and
fixed
i l l i t i c smectite
octahedral
reaction
arrangements be
by
''hexagonal"
and
prismatic
(K,
K-fixation
mechanically
of
performed
original
by
configurations;
interlayer
the
Fe-complexes
of
lack such
cations
52% b y
and
in
smectite
a
experiments,
that
drying
Al-
K-ions
drying
more
four
and
fixation
interlayer
dehydrated
drying
and
fixed,
as
procedure,
and
is
K-exchanged
defined
standard-exchange
1 Ν NaCl. only
of
being
different
Κ
drying
fixation
chemical Recent
permitted
a
14.
EBERL ET AL.
Materials
and
Smectites
with
charge
in
a
for
range
were some
II;
formulae
of
Table
has
starting
in a
interlayer
(46).
Coarse-grain
washed
by
times
to
starting
solutions, could
followed
in
not
be
overnight; about
1
washed
and
in
the
AgN0
was
accomplished
by
Sr-exchanges
0.1
dialyzed
putting
Ν
as
discussed
were
300
without
shaking;
several prior
2
WD
to
each
A
drying
Na-K
100 mL o f
0.05
by Ν
paper by
is
for
preparations WD
cycles
solvated
in
treatment,
and
electrolyte additional Clays
exchanges
Illite XRD
contents
but
contained Oxygen Mayeda
relative
to
and
Ν
of
SrCl2
then
for were
each
not
or
Sr.
to
day
at
Kinney
dispersed
by
powder
names
in
with Clays
XRD
in
this
endorsement glass-slide
Clays
analysis,
were
In
ratios.
subjected no
to
additional
processed and
centrifugation,
largely
per
oriented, (42).
in
shaking
the
clay
trade
investigated Na
60°C. by
constitute
of
prior
at
for
investigated
glycol
with
day
NaCl/KCl
drying
conducted
completed
of
a
were
completely was
use
in
solution
then
and
separated
in
given
dialysis. from
these
analysis.
of
the
90°C mL o f
150 mg o f
does
dispersion,
the
(43,
measured
of
the
were
and 20
determined
were
washed
44)
characteristics were
60°, with
different
K-minerals
XRD
Srodon
reflections),
and
to
was
ethylene
were
shaking
products
experiments
Survey)
exchange
contents of
only
water
by
with
prior
techniques
that
after
solutions
processed
K-minerals
from
distilled
Sr-exchange by
completed
system;
with
several chloride
accomplished
30°,
shaking
Geological
by
until
first
the
chloride
0.1
1 WD c y c l e
products
D-500
of
1 Ν
in
dispersed
having
identification
U.S.
and
overnight
solutions
Siemens
the
were
isotherm
Solid-experimental (automated
at
were
cycle,
samples
shaking
together Most
cycles
exchange
montmorillonite
clay
clays
the
in
then
several
previously.
boats.
experiments,
60°C.
of
The
were
and
washed
exchanges,
by
X-ray
spectroscopy
clean
Experimental
conducted
mg
polyethylene-weighing
were
solutions.
The
by
products
dialysis,
test.
3
the
smectite
ground,
overnight
by
The
of
Sr-saturation
chloride
finally
given
all
each
then
to
or
shaking
by
WD e x p e r i m e n t s oven,
and
products
subsequent
hour
were
Na-,
1 Ν
and
for
experimental
Κ
K-,
more
III.
chemistry
overnight,
soluble by
Table
distribution.
layer
I)
purified are
atomic-absorption
(Table
achieved
detected
experimental
in
layer-
Chemical
(44),
although
and
by
water
readily
two
been
compositions
smectites
water,
had
Jackson
2:1
in
I).
presented
for
chemistry
by
distilled
variation (Table
layer-charge
analyzed
material.
was
of
smectite,
distilled
( C0
d Ή O co co m i» ·» rH C0 00 C0 *H S d w < rH eu co PM · d co eu CO 4-> CO CO I co «
VI d o o MH -H 4-> C0 U
§
5-1 CO
>» co «Ο X eu
u o o
d eu VI 00 N H X ) CU
4-> 4-» CO M 00 d
u o •H U P*
co
co
T3 CO CU rH 4-> Vl co eu eu 4-> vi d H Ή
III.
B
Garfield
3 . .95
3 . .97
3 . .92
4 .. 0 0
Otay
Texas
an
give
to
Black
be
ideal
0
0
0
0
0
0
0
+
as
as
(63),
0 .. 1 5
0 .. 0 3
0 ,. 6 4
1, . 3 6
3
+
0, . 0 2
0 .. 2 2
0 .. 1 8
0 .. 0 7
0 .. 0 8
Mg
3
NA
NA
NA
NA
NA
0
and
Κ
subtracted
and
0 .. 0 4
0 ,. 0 1
0 .. 0 1
0 .. 0 2
0 .. 0 2
0 .. 4 7
0 .. 0 2
0 .. 5 7
0 .. 0 4
0 .. 0 1
0 .. 0 2
from
for
0 .. 0 9
0 .. 0 2
0 .. 0 1
0 .. 0 6
0 .. 0 1
0
0 .. 0 9
0
0 .. 0 8
0 ,. 0 9
0 .. 0 4
0
0 .. 1 3
0 .. 2 0
0 .. 2 1
0 .. 2 6
0 .. 2 2
0
0 .. 1 5
0
0 .. 2 3
0 .. 1 8
0 .. 2 5
0
Sr
the
Based
from
in
Table
(14).
69
61
100
87
67
96
85
4
4
30
100
0
(Percent)
Charge
Octahedral
analysis
Kinney
(Equivalents)
Na
Interlayer
Otherwise]
Experiments,
Noted
Drying
Unless
0 .. 4 6
II,
(51),
0.40
NA
NA
NA
NA
NA
Β from
material,
Garfield
amorphous
for
0 ,. 3 1
0 .. 3 0
0 ,. 4 1
0 .. 7 4
0 ,. 3 1
0 .. 4 6
2, . 6 1
0 .. 0 2
0 ,. 1 1
0 ,. 1 4
0 ,. 5 6
0 ,. 0 1
Li
Table
i n Wetting
anatase.
0 .. 0 4
0 . .07
0 . .01
1. . 8 3
1. . 8 9
1. . 2 2
0 .. 0 8
discrete
1, . 4 9
1. . 5 3
1. . 5 2
1, . 2 5
1, . 6 5
1. . 4 7
0
F e (Equivalents)
1. . 9 9
Al
in
Used
Data
Octahedral
from
Smectites
occupancy.
present
from
tetrahedral
3
0.16
0
0
0
0
present
0 .. 1 1
0 .. 1 7
0
0 .. 0 8
0 .. 1 3
0 .. 0 3
0 .. 0 5
0 .. 3 9
0 .. 5 4
0 ,. 3 2
0
0 ,. 5 2
Jack
presumably
Si0 ,
3.5%
4
2
analyzed.
Not
for
considered
3
is
Formulae
2
Ti
3 ..89
Wyoming
1
3 .. 8 3
Umiat
4
3 .. 8 7
Montmorillon
2
Hectorite
Kinney
3 . .45
3 .. 4 6
A
Garfield
2
3 .. 6 8
3 .. 4 8
Ferruginous
2
4 .. 0 0
Jack
1
F e
(Equivalents)
Al
Tetrahedral
Si
for
Calculated
Formulae
[Formulae
Structural
Cheto
Black
Smectite
Table 1 0
(OH)
Charge
Layer
Total
0
II
to
0 .. 3 6
0 ,. 4 4
0 .. 4 1
0 .. 6 1
0 ,. 4 4
0 .. 4 9
0 .. 4 1
0 .. 5 7
0 .. 5 6
0 .. 4 6
0 ,. 5 6
0 ,. 4 7
(Equivalents)
on
14.
Potassium
E B E R L E T AL.
Experimental Behavior of
K-Exchanged
smectites
randomly
Smectites
(Table
Those
patterns
I/S
for layer
charge
to
low a
smectites.
XRD from
were
displaced
toward
was
for
3-component
the
graph
43).
lower
energy
led
studies. smectite A
K/Na
identify
XRD
given
exchange
positions the
i l l i t e
contents
and
ratio
of
0
to
This
of
for
the
0
003
glycol
increased,
At
ratios
between
K/Na
constant,
interpreted layers. out
as
At
of
and a
K/Na
the
characteristics observed. towards
In
All
of
it is
was
the
when
mildest
100% s m e c t i t e saturation illite-like as
a
measure
of
burial or
the
that
of
these
WD
given
in
evident
001 of
a
the
as
the
Κ
(42).
remained which
in
evolved above,
could
began
is
expanded
discussed
is
K/Na
of
content by
of
sample
exchange
to
be
migrate
expected
a
single,
overnight
sufficient
to
w h i c h means
test
because,
during during are
exchange
(1.4
for
the
Na,
(49);
chemical
analysis.
affected
re-expanded
solution. with
the to
nm)
treatment
unlike
I)
NaCl
restore
dialysis not
1 Ν
reexpanding
vermiculite-like This
(Table
with
layers.
0.1
and
is
on
the
not
therefore,
Sr
Illite
significantly
Then SrCl2
K-Kinney
1.7-nm
was
layers
a
used
replaced
gives
by
to
glycol
unstable
subsequently
Sr
Ν
a
formed
either
by
better the
by Na-
procedures.
K-Smectites
Table
From
XRD s p a c i n g s
as
smectites times
nm)
Figures
the I/S;
35/65,
the
CEC
Na
the
determine
increase,
reflection
(1.0
experiments from
for
to
interstratification
the Na/K
to
with
function
spacing
Na-K
i l l i t e of
Na-Kinney
of
glycol for
40/60,
both
Sr-exchange
Response
than
four
treatment
diagenesis
the
a
2).
content
continued
possible
K-exchanged
structure,
ions
Jack
layers.
exchanged
standard
hydronium
at
in
previous
plotting
used
(Figure
35/65,
3-component
angles
determined
the
greater range
1.4-nm
of
completely
and
by as
graph
expected
replacement
particular,
greater
development
a
I/S
and
is
spacing
continued
of
with
Na-Black
using
peaks
i l l i t e
49%,
25/75
ratios
8A
hydration
mixed-layering
followed
XRD
on
for
the
as
glycol
two-theta
was
solution
about
layers
determined
005
spacings
expanded
Figure
and
3-component
and
25/75,
to
of
evolution
exchange
about
from
was
evolution
content.
peaks outside
1.
isotherm
the
K-
or
higher
agreement
was the
displaced two
side
(see of
001
was
latter
left
I/S
for
the
diffuse;
005
The
ion
in
patterns
in Figure
study
an
is
in
the
more
the
extreme
with
that
much
mixed-layer
K-smectite
re-expansion,
ratio
nearly
the
complete
Κ
increased
on
probably
interstratifications
in
two-theta.
example,
to
changing
plot
of
1.0/1.4/1.7-nm
swelling
and
gave
Those
distributions
was
angles;
of
to
Na-K
increasing
higher
002
for upon
Wyoming)
layers.
3-component
the
All
minerals
3-component
2-component,
For are
smectite
to of
the
angles
system
used
Saturation
as
Drying.
(e.g.
heterogeneous
angles;
and
characteristic
i l l i t e
layer-charge the
toward
towards
charge
percent
for
of
higher
displaced
the
of
patterns
Wetting
patterns
mixed-layered
identified
This
those
XRD
layer
few
heterogeneous
differed
slightly
303
Without
gave (RO)
of with
interstratifications. related
003
I)
interstratified
K-exchange. higher
in Smectite
Results
of
the
Fixation
3
to
are and
IV:
WD C y c l e s given
4.
The
in
i n Water
Table
IV;
following
at
60°C.
sample patterns
Results
of
XRD p a t t e r n s
are
of
reaction
are
350
0
1.
XRD
for
=
(
'
30
'
L
labeled
sample
Β
i n nm.
50
sample
that
patterns
Jack
glycolBlack identical
on K-exchanged
=
1
ethylene
40
K-exchange and
of
radiation; sample;
effect
C u i
THETA (DEGREES)
Peaks
Na-exchanged
K-exchanged
showing
then Na-exchanged.
found
were
was
A
TWO -
Si
patterns
'
samples)
1Ï
smectite.
solvated
Figure
'
1.51
14.
EBERL ET AL.
Potassium
Fixation
in Smectite
305
19.01 100 95 18.6
17.8
1 7
ω
Λ
17.4
LU LU CE
O
LU Q
17.0
g
16.6
16.2
15.8 GLYCOL COMPLEX THICKNESS (nm) 15.4 25.8
26.2 TWO
Figure
2.
Plot
glycol-solvated Ν
Na
with
+
Κ
having
XRD p e a k
exchange
percentages
percentage
of
samples) of
i l l i t e
crystallite
26.6
- THETA
positions
for
Kinney
solutions. Κ
in
layers
thickness
(CuK
radiation;
smectite
treated
Experimental
solution. and
27.0
(DEGREES)
The
graph,
glycol-spacing of
1-14
points
layers,
for is
used
ethylene with
are to
0.05
labeled determine
illite/smectites from
(42).
GEOCHEMICAL PROCESSES AT MINERAL SURFACES
306
ι
«
1
1
r
·
1
•
TWO Figure
3.
samples) 100
WD
indicates Jack
XRD p a t t e r n s for
in
a trace
of
Peaks
water
«
1
•
1
'
1
·
1
·
r
THETA (DEGREES)
(CuK
Sr-exchanged
cycles
pattern.
-
1
radiation;
K-smectites at
60°C.
Rl ordering labeled
is
i n nm.
ethylene
that A
have
low-angle
marked
glycol-solvated
been
subjected
shoulder
by a t i c k
on t h e
to that
Black
EBERL ET AL.
14.
Potassium
Fixation
in
Smectite
307
300
TWO Figure
4.
XRD p a t t e r n s
samples)
showing
that
been
has
in
0.5
in
0.5
Ν Ν
KOH,
2
Ε
100
WD
cycles
in
Β
=
WD in for
to
1
Sr
cycles
0.5
Peaks
of
a
Ν
time
in
0.5 2
0.5
N
with
D
nm.
=
1
100 with
glycol-solvated
K-Kinney
Ν NaCl;
KC1,
equivalent in
for
treatments.
exchange; in
ethylene
contents
various
CaCl ,
labeled
(DEGREES)
radiation; illite
4 0 WD c y c l e s
with
100
suspension
Sr-exchange.
=
THETA
(CuK
range
subjected
NaCl;
CaCl ;
a
-
100 WD
cycles
C =
1 0 0 WD
cycles
WD 1
cycles
100
in
Sr-exchange;
Sr-exchange; to
smectite
A =
WD
G =
clay
cycles,
0.5
Ν
F
=
left
with
1
51 23
3 4
1 1 0 1 5
1 1 1 1
0 5 10 15
7
8
9
8 4 4 3 3 4 4 4 4 4
1 1 1 1 1 1 1 1 1 1
100 100 5 10 15 20 25 30 40 50
K-Hectorite
K-Kinney
19
20
21
22
23
24
25
26
27
6
100
17
K-Garfield
21
0
1
100
16
18
35
0
1
75
15
37
37
35
35
34
36
33
29
20
16
36
34
1
35
3 0
1
40
34
50
1
1
30
12
33
30
14
0
1
28
32
31
13
0
1
20 25
10
11
6
19
8
4
100
K-Ferruginous
K-Cheto
5
9
100
52
Κ
6
Na
Meq p e r
0
4
3
Chemistry of with
132
80
82
83
86
83
80
87
89
92
67
123
124
125
122
118
126
125
125
91
115
105
78
104
100
106
100
101
96
97
105
102
103
30
30
29
28
28
26
26
22
12
26
29
43
41
41
41
41
37
36
36
38
33
0
15
0
0
43
120
103 91
2
to
Layers
(Percent)
Illite
SrCl
Subjected
41
Ν
135
131
68
68
66
68
66
68
66
64
72
71
83
93
81
119
137
Total
Sr
0.1
K-Smectites
g Oxide
122
100
Then Exchanged
3 1
Exchanges
0
Sr
of
and
Interlayer 60°C,
Number
at
and
1
Jack
of
WD C y c l e s
Number
Layers i n Water
100
K-Black
Sample
Illite Cycles
100
2
1
Number
of
and D r y i n g
Percentage
Wetting
IV.
Reference
Table
x
Not
3 8 97
K-Wyoming
analyzed.
43
24
1
100
102
79 63
20
3 10
3
100
10 109
74
29
6
1
0
11
101
105
2
95
81
22
3 1 4
22
105
63
38
4
1
0
26
102
132
73
3
97
51
8 1 2
51
131
71
56
4
5
17
137
112
88 120
1
13
21
3 4
2
27
111
69
101
0
9
33
32
107
127
123
1
40
1
2
4
1
100
0
100
100
0
100
100
0
100
100
0
NA
NA
1
NA
79 85
39
3
1
40
4
1
42
K-Umiat
K-Texas
K-Otay
K-Montmorillon
100
100
75
41
40
39
38
37
36
35
34
33
32
31
30
29
28
S'
3
S
m το r m H
DO
m
310
GEOCHEMICAL PROCESSES AT MINERAL SURFACES (1)
WD
cycles
cation (2)
A
stabilize
with
regular
centage
1.0-nm
substantial decrease
of
in
fixed
layers
against
hydration CEC
Κ
(meq
and
exchange
by
a
energy. Sr)
occurs
percentage
of
as
the
illite
per
layers
increases. (3)
The
quantity
and
1
from
of
i l l i t e
Sr-exchange Tables
smectites
is
III
and
with
a
that
have and
perfect
i l l i t e
layers
expected, on
may
The
total
not
changed
for
that
2:1
the
of
the
possible
most
of
Rl
and
Kinney
the
a
001
very
by
of
WD
is
more
by
cations
process,
does
is
thereby
not
change.
These
to
i l l i t e
is
simple
layers, are
dehydration
rather
randomly
Black
(Figure
between
weak
not
depend
distribution.
interlayer
reaction
WD
the
sample XRD
is
also
than
a and
by
an
charge.
produced
exception
quantity
distribution
the
charge
smectite
layer
ordering
samples,
angles,
of
2:1
I/S
i l l i t i c
partial
these
the
in
octahedral
charge may
do
charge
smectites.
of
caused
than
the
layer-charge
the
reaction
61%
layer
charge
by
layer
with
reaction
beidellitic
that
rearrangement All
as
that
significantly
transformation
with
the
suggest
increase
such
charge
better
between
and
this
milliequivalents
indicating data
because
indicate
heterogeneous
WD
(data
although
tetrahedral
montmorillonite by
5),
octahedral
of
correspondence
factors,
5
of
cycles
charge
Figure
relation
component
100-WD
layer
in
this
formed
however,
other
Figure
one
after
to
component
large
(beidellites of
(4)
a
formed
plotted
follow
charge).
A
IV
large
(montmorillonites) those
layers
proportional
Jack
4),
i l l i t e
reflections
superlattice
both
and are
interstratified,
sample of
(Figure
which
smectite
displaced
reflection
is
3)
show
and signs
layers. towards
visible
For larger
at
small
angles. The
stability
investigated exchanges (Table with all
to
a
except Kinney
is
1
exchanges
NaCl
i l l i t e may b e
layers of
The the
comparable with
i l l i t e
rotation
III)
equations
(29,
layers
the
use
the
WD
to
in
clays
those
illite
which
formed layers
is
a
WD,
to
layer-charge
the
was
measurements
by
b
of
from
(Table
V)
50):
a =
b
observed
b. , ,(Si, Al ) ideal 1-x χ
=
b 9.15
ideal +
0.1
0.74x
the
SrCl2
of
four
Thus,
the
Sr-exchanges diagenesis.
one
the
and
three
stability to
of
original
but,
based
on
mean
angle
of
(Figure
6).
structural by
Ν
use
neither to
in
experiments
burial
smectite
calculated
preserved
(44).
location,
roughly
of
the
between
correlates
original
available
three
measure
by
correlate (a)
after
SrCl2
significantly
three
I/S
was
was
were
of
WD Ν
Exchange
diagenetic
nor
Cos where
that
study
2
rotation
and
i l l i t e
smectite.
to
SrCl ,
of
sample
by 0.1
decreased
than
in
does
layers
treatment
formed
data,
tetrahedral
(Table
Ν
sufficient
Jack
stability
charge,
limited
tetrahedral of
0.1
produced
additional
stronger
change
layers
smectite-layer very
i l l i t e
showed
used
percentage
exchanges
which
of
measurable
slightly remaining
layers two
for
Black
sample
exchanges Ν
a
but the
i l l i t e
applying
quantity
treatment,
WD
the by
smectites
The
samples
with
WD
IV).
this
of
further
the
Angle formulae
following
14.
EBERL ET AL.
Potassium
Fixation
311
in Smectite
60
For Montmorillonites: % ILLITE = 157C- 45
-0.3
-0.4
-0.5
LAYER (EQUIVALENTS Figure
5.
Percentage
K-smectites
subjected
Sr-exchange. octahedral 69%
i l l i t e
o r more
(C)
HALF - UNIT
layers
versus
t o 1 0 0 WD c y c l e s
Numbers charge.
PER
Best
octahedral
i n parentheses
-0.7
-0.6
CHARGE
CELL) layer
i n water refer
charge
a t 60°C
t o percentage
f i t line
i s for montmorillonites
charge.
Data
from
for and 1
Tables
III
o f
having
and
IV.
312
Figure
GEOCHEMICAL PROCESSES AT MINERAL SURFACES
6.
percentage
Stability of
Sr-exchanges rotation.
change is
Data
of
i l l i t e
layers
i n percentage
plotted from T a b l e
against V.
formed
i l l i t e or,
the
by
layers angle
WD m e c h a n i s m :
between of
1 and 3
tetrahedral
EBERL ET AL.
14.
Table
V.
Data
100 W e t t i n g
Potassium
Used and
to
Fixation
in Smectite
Construct Figure
Drying
Cycles,
Times
Original
and
With
Ν
SrCl
K-Smectites
^ideal
Once
Submitted and
2
Illite
Layers
(Degrees)
(Percent
0.899
0.925
13.6
100
Cheto
0.898
0.915
11.1
63
Ferruginous
0.907
0.921
10.0
33
Garfield
0.914
Black
Jack
2
6
39
Hectorite
0.909
0.916
7.1
NA
Kinney
0.897
0.916
11.7
73
Montmorillon
0.898
0.917
11.7
37
Otay
0.899
0.917
11.4
50 50
Texas
0.897
0.915
11.4
Umiat
0.898
0.918
12.0
70
Wyoming
0.898
0.917
11.7
NA
*(%
i l l i t e
layers,
1 Sr-exchange) (%
2
a
3
Not
measured
directly
analyzed.
i l l i t e (51).
-
layers,
(% 1
i l l i t e
to
Three
α
(nm)
Clay ^observed
for
Then Exchanged
0.1
Smectite
6
313
layers,
Sr-exchange)
3
1
Change)
3
Sr-exchanges)
314
G E O C H E M I C A L PROCESSES AT M I N E R A L
This than
method
about
7°,
for
and
109°28'.
A
expected,
because
holes
in
the
are
holes
2:1
relationship the
are,
basal
oxygen
the
less
Sr-exchange.
Alpha
would
be
analysis
for
is
beyond
Tetrahedral for
a
and
the
in
completely.
The
coordination that
does
not
the
lie
a,
could
on
of
of of
in
in
The
smectite effect
has
a
to
Similar resolve
42%
The decrease
in
to
50
Fixed
Thus, it
such
in
than Of =
6°
in
are
tend
an
to
to the the
bind
presence
Κ or
smectite-crystal
prismatic
or
interlayers, affect
to
affecting
the
WD
the
addition
factors
and
Κ the
(51),
belongs in
would
the
into
perhaps
measured
which
the
octahedral
and
Κ
to
various
availability
(V.
are
the
shown
first
slightly
more
the
layer
much
smaller
degree
and
the
to
other
layers
of
factors
iron-rich
i l l i t e a
given
Ferruginous
(Table
III).
of
tetrahedral
This
tetrahedral rotation
mentioned
smectites
the
cycles.
for
the
component
other
for of
100 WD
though
charge
larger
Most
although
after
i l l i t e even
i l l i t e
7.
2 0 WD c y c l e s ,
K i n n e y does
smaller
towards
in Figure
are
for
above.
needed
to
with
WD
power that
equivalents)
cycles,
are
curve, plot
on
actually
than
are
enough
each
and
drying
subjected
shaking,
of
cycle
to
compared
32%
for
speeds
reaction.
6 4 WD c y c l e s
with
K-Kinney
fixed-interlayer
K,
i l l i t e
content
with
very
Sr-exchange
greater
to
smectite
increasing
by
a
prior
30%
for
subjected
produced K-Kinney to
75 WD
shaking.
cations
samples
not
water
equivalents with
removed
Of t h a t
interlayer
rather
transformation
produces
with
K-Kinney
without
8).
of
case,
role,
increasing
the
to
sample,
layers,
not fits
than
slightly
a
i l l i t e
subjected
angles
dominant
to
sheet holes
question.
example,
cycles,
in be
smectite
experiments this
Shaking For
to
slightly
the
K-O
adjust
the
factors,
Two
to
close
because
could
the
structural
30°
interlayers,
that
the
related
Ferruginous
is
either
or
size;
tetrahedral
other
charges,
smectites
formed
still
be
6
dehydrated
layers
size,
(30).
small,
ordering
lead
of
WD c y c l e s
may
charge, the
are
Ferruginous of
layer
to
hole
communication).
and K i n n e y
appears
a
of
into
are
required
this
a
But
play
the
2:1
kinetics
layers
number
in
the
personal
Ferruginous
The
Κ
small
Sr-exchange.
could
are of
holes
Figure
highly-charged
for
distortions
i l l i t e
even
to
which
coordination Drits,
or
Κ
in
system.
three-dimensional
structures,
content
curve
ions
detailed
larger
in
with
smaller
work.
angles for
The
Κ
a
coordination,
sample,
heterogeneous
strongly
absence
A.
the
large
is
ditrigonal
can penetrate
hole
such
clays
symmetry;
of
stability
layers.
the
present
ditrigonal
different
availability more
of
greater angle
the
indicator
normally
12-fold
Garfield
influence,
presence
so
into
reason
energetically
is
2:1
the
But
Rotation
hexagonal
6-fold
the
Of i s
layer
Κ ions
directly the
i f
smaller
approximate
of
sheet.
nearly
the
dioctahedral
between
hole
approaches more
in
the
of
layers.
scope
size
octahedral
enters
measure
the
Of i s ,
susceptible
an
i l l i t e
rotations
misfit
hole
to
i l l i t e
dehydrated
more
only
the
and
planes
is
generally
0(apical)-Si-0(basal)
α
the
deeply
the
better
lengths
applies
a
ideal
between
larger
thus,
it
an
the
layers;
bond
estimating assumes
SURFACES
one,
as
depicted
the
extreme
gave
which
holes
in
a
(Tables
is the
IV in
small
the
the
The
figure.
lower
impossible
per WD
end of
of
of
Na
that
Calculations the
curve
to
was
roughly (at
fixed-interlayer
planes
layer (Figure
relation
structurally,
oxygen
i l l i t e
samples
component
and V I ) .
equivalents basal
cations for
for 1.0
cations
because
accommodate
there more
14.
EBERL ET AL.
Potassium
50 ι
Fixation
!
0
1
20
40 NUMBER
Figure
7 .
versus
number
after
OF
î
Γ
60
80
1 Sr-exchange.
Data
percentage
f o r Ferruginous from T a b l e
100
CYCLES
K i n e t i c s o f WD i l l i t i z a t i o n : o f WD c y c l e s
315
in Smectite
IV.
i l l i t e
and Kinney
layers
smectites
316
GEOCHEMICAL PROCESSES AT MINERAL SURFACES
High pH Kinney
-1.66 % ILLITE = 7.1C R = 0.72 2
-Ι Ο.3
0.4
FIXED
0.5
0.6
INTERLAYER
CATIONS
(EQUIVALENTS Figure
8.
interlayer Solid
circles
circles
=
iron-rich data
Percentage cations =
i l l i t e
PER
aluminous
smectites
with
0.9
ILLITE
HALF - UNIT
layers smectites
smectites
0.8
PER
versus
(Na + K ) p e r i l l i t e
aluminous
i n Tables
0.7
with
layer with 2
1 Sr-exchange.
I I I , IV, V I , and VIII.
1.0
LAYER
(C)
CELL)
equivalents [based
on 0
of 1 0
1 Sr-exchange.
o r 3 Sr-exchanges. Points
fixed
(OH)2l·
calculated
Open X = from
EBERL ET AL.
14.
than in
1.0
equivalents
determining
in
Figure
i l l i t i c that
The
cation by
penetration 2:1
clays, The
as
9).
clays Effect
of
Fixed
to
clays.
of
the IV
errors
The
data
increase
and
in
Figure
required
to
larger
Table
Effect
the
the
of
8
at
7),
stabilize
reaction of
Submitted
to
Solution
Once W i t h
Reference
Meq
0.1
in
on
clays
is
layer
for
solution
Table
the
SrCl
ι>
100
per
latter
changing
Cycles Ν
randomly diagenesis
(53).
given
Drying
for
i l l i t e
of
is
above.
the
per
deeper
iron-rich
burial
for
layers
produced
the in
that
by
in
fixed
observation
found
from
effect
and
lower
to
mentioned
Composition
40 W e t t i n g
Exchanged
holes
K-Kinney
a
related
content
The
of
at
curve
tested
similar
equivalents
50% i l l i t e
the
clays
(glauconite)
bentonite
cation
Composition.
the
A
distinct
0.55
than
can.
factors
is
left
WD
layers
basal
from
about
by
may b e
other
produced
less
Solution on
clays
the
to
to
iron-rich
layers
illite
interlayer
contain
VI.
is
that
effect
Figure
I/S
composition
K-Kinney
as in
constant
that
attributed
(Table
mostly
This
into
well
interstratified (Figure
cycles
i l l i t e
iron-rich
Κ
pattern
relatively
is
smectitic
cycles
plot
form
(52).
of
WD
aluminous
for
diagenesis
excess
consideration
indicating
can
than
made
317
highly
WD
samples
thereby
content
been
a
increasing
iron-rich 8,
The in
from of
Smectite
layers.
experiments
has
K-ions.
number
i l l i t e
Figure
these
with
greater
in
contents
indicate,
content
a
Fixation
of
i l l i t e
8
low-charge in
Potassium
at
VI.
The
Reaction 60°C,
and
of Then
2
Illite
Oxide
Layers
Solution Number 26
Water
44
0.5
Ν
45
0.5
N KC1
46
0.5
Ν
pH
47 48
Average
of
two
presence
of
0.5
reaction
rate
CaCl
2
the
0.5
Ν
in
KOH
in
illite is In from
layers
greater
formed
by
the
chemical
experiments
Sr
Total
4
37
83
124
30
5
35
82
122
32
3
40
81
125
31
3
27
96
126
23
3
32
85
121
30
6
71
77
154
48
N KC1,
with
significantly
the in It
slowed
The was
this
sample
that
expected
untreated
Kinney
data
data
(Tables
underwent
(Table IV
is
to
and
about
significant
effect The
exception, did
the
not
high
average
of
in
Ν
the
change pH
run
that
the
charge
Figure
this
for
8,
and
expandability
curve
expanded
on
0.5
whereas
indicating
plotted
(Figure
layers
9).
increased
-0.52.
support
VI)
is
diagenetic
for
VII)
one
The
clays
no
reaction,
charge
thereby
the
charge
of
With
altered.
had
i n water.
exception
for on
3.6)
rate
layer
(0.57)
better
isotope
(pH made
rate.
increased,
layer
average
the
total
reaction.
fits
HC1
the
that
charge 2:1
and
experiments
increased
indicate
layer
the
for
Oxygen
0.5
compared
than WD.
addition, -0.49
Ν NaCl,
during of
Κ
analyses.
VI
which
composition
(HC1)
solution
Table
significantly (KOH)
2
Ν KOH
as
solution
data
CaCl
3.6
0.5
1
NaCl
(Percent)
Na
that
chemical
conclusions
clay
in
the
reaction,
drawn high
from
pH,
whereas
WD clay
GEOCHEMICAL PROCESSES AT MINERAL SURFACES
318
60
ι
-
ι
—
ι
ι ""•
1
1
i 50
• —
•
• •
•
-
•
•
• ·
• < »
•
• •
• 10
1
0 0.3
0.4
0.5
FIXED INTERLAYER (EQUIVALENTS
Figure
9.
interlayer
Percentage cations
illite/smectites from
data
i n
formed
(53).
i l l i t e
per i l l i t e
L
0.6
1
0.7
L
0.8
0.9
1.0
CATIONS PER ILLITE LAYER PER
HALF - UNIT
layers layer
by diagenesis
versus [based
CELL)
equivalents on 0
1 0
of
(OH) ]
i n bentonites.
2
fixed
for
RO
Calculated
Jack
Ferruginous
Cheto
Umiat
Hector
Texas
Montmorillon
Otay
Black
Kinney
Smectite
of
Isotope
Various
δ 1 8
0
2.0
1.2,
1 6 . .7
16. 5
100
12 . 8 12 . 7
12. 7 12. 6
21. 5, 15. 2, 1 3 ., 8 , 1 7 . 1, 17. 4, 1 2 .. 8 , 1 2 .• 7 ,
Water Water Water Water Water Water Water
100
0
100
0
100
0
100
17. 2, 16. 9 ,
14. 5, 14. 2,
22. 3, 20. 8,
22. 2,
Water
0
21.7,
2 1 .. 7 ,
2 1 ,. 4 21 . 2 2 1 .. 7 ,
13 . 9 17, . 2 17 . 1
1 7 .. 4 1 7 .. 0
14, . 7
2 2 ,. 0 2 2 ,. 0 2 1 .• 9 ,
1 3 .. 7
1 4 .. 3
21.7,
2 1 .. 7 ,
2 5 ,. 7
2 6 ,. 0
25.8
Water
100
2 5 ., 6 ,
2 5 .. 0 26.8
26. 2, 26. 0,
2 5 .. 5 ,
25. 4, 25. 5,
25. 0
Water Water
0
Water
100
2 6 .. 3
16. 9 , 26. 3
Water
0
1..5 1 7 .. 4
17. 8
17. 0,
Water
1.3,
0
1.2,
2.0,
Water
100
1.. 6
1 6 . .0 2.1
Water
Ν KOH
0
0.5
1 4 . .1
40
1 3 . .8
1 4 . 1, 1 4 . .2 1 5 . 9 , 1 6 . 5 , 1 5 . ,7 1.6, 1.6, 1 .4, 1.5,
13. 9 ,
Water
100
1 4 . .1
1 8
13. 8
14.4
δ
Average
13. 8,
0
Smectites
Water
1 4 .. 6 ,
of
Measurements
for
13. 4,
Data
Water
Composition
Solution
Oxygen
0
VII.
64
WD C y c l e s
Number
Table
320
G E O C H E M I C A L PROCESSES AT M I N E R A L SURFACES
wetted
and d r i e d
Table
VII
water
either
that
the
lighter, on
layer
which
is,
edges
Sr-exchanged of
the
values
larger
for
high
became
of
Wyoming
to
XRD
thereby
to
pattern Otay
at
high
smectites
by
charge
is
The X-rayed
this
to
1.0/1.4/1.7-nm
excess
to the
with
42% f o r
the
after
differed
by only
cycles (no
CaCl
a
twice
with
0.1
products results
Table are
with
in
IV.
at
The
with
0.5
layers,
reaction
shown in
a
low-charge
i n which
More
to
that
solubility
reaction
a
was
work
of
layer
is
needed
products
Ν
after those
for not
VI),
when
3-component experimental
2
two
1.0-nm
component
layers
well
one
Sr
saturation.
given
in
Table
NaCl But
40-
from
VI 63
experiments, the
increase
the
and
the
the
to
71%
and
stability
with
WD
showed
of
number
from these
of
100-cycle
WD runs
illite. had
formed
SrCl
Table
were
increased
the
of
and C a C l
containing
VIII
VIII).
after
are
erratic
effect
K-Kinney,
on
the
which
was
3 0 ° , 6 0 ° , and 9Q°C,
(Table
2
little
from
at
not X-rayed
The
(Table
not
data
a
and then
Unfortunately, single
directly
resulting
the
Sr-saturation; comparable from
to
the
90°C
unexplained. Minerals.
sparingly
natural
Na-Kinney
the
formed
however,
6 WD c y c l e s
were
K-Bearing
and
be
The NaCl
than
layers
saturated
experiments
0
were
clay
time
have
characteristics
Temperature
i l l i t e as
simulate
did
few p e r c e n t
many
Na-Kinney
have
Sr-exchange,
as
in
of
The increased
experiments.
2
to
therefore,
Otay
for
55)
chemical
Sr-exchange)
layers
one
of
experimental
8
in
giving
42% i l l i t e
Si substitution.
cycles
subjected
Reaction
to a
remaining
Temperature.
percentage
those
1 Ν KOH.
KOH e x p e r i m e n t a l
1 0 0 WD
i l l i t e
cycles:
of
for
number
more
and
additional
Effect
Al
(8,
smectite
layers,
length
about
can
Sr-saturation,
content
40
1
substantial
Sr-exchanged.
the
essential
layers
interstratification.
of
i l l i t e
to
in
and
form
not
interstratifications,
experiments
30
them by
K-Otay
t h e same
to
studies
Sr-exchange,
prior
between
for
i l l i t e
K C 1 , HC1, and
1.0/1.7-nm
δ
suggestion.
prior
products
reacted) for
4 0 WD c y c l e s
50% i l l i t e
treatment,
WD i s
p H may l e a d
increased
confirm
the
The Kinney
indicating
and
than
reacted
that
of
high
the
Previous
boiling
at
times.
the
by
scatter
after
thereby
were
from
favored
in
atoms
that
p e r mg c l a y
2
drying
m i l heavier
greater
WD,
pH.
0
decrease
K-Wyoming
suspension
number
and S i
that
in
slightly
oxygen
water
is
i n 0 . 5 Ν KOH, and t h e n
after
without
significant
per
of
difficulties
(micromoles increased
indicating
chemistry.
form
demonstrating
i l l i t e
2
2 0 WD c y c l e s
KOH, b u t
in
layer
exchange
in
distilled
became
interlayer
a
Data
in
thereby or
possibility
solution,
experiments,
reacted
destroyed.
to
2:1
an
the
and o f to
did not.
cycles
change,
to
of
yields
experimental
not
latter
clays,
however,
other
subjected
Al
oxygen
subjected
pH
In
Ν
The
WD
experimental
a l l
clays
alteration
weak
samples.
to
isotopically,
did
related
or to
removing
Sr-saturated
smectite, the
unchanged
perhaps,
solutions
subjected
chemistry
(54),
in
experimental clay
remained
encountered finding
other that
2:1
crystal
for
in
indicate
room
conditions. temperature
i l l i t e
layers
were
i l l i t e
layers
formed
found when
WD
soluble
in
When without the
experiments
K-minerals
K-feldspar WD f o r
as
experimental
muscovite
was
with
were
shaken
was long
mixtures
to
shaken as
product. with
of
undertaken
with
1 year, Nor
Na-Kinney
no
were for
14.
Potassium
EBERL ET AL.
Table
VIII.
K-Kinney
Effect Submitted
of
Fixation
Temperature
to
Wetting Twice
Reference
Temperature
in Smectite
Number
on
the
Formation
and Drying
With
of
321
0.1
Ν
Meq
per
Cycles,
SrCl
of
I l l i t e
and Then
Layers
i n
Exchanged
2
100
g Oxide
I l l i t e
Layers
WD Number
(°C)
Cycles
49
30
Sr
Total
(Percent)
0
4
9
113
126
0
1
4
13
110
127
7
51
2
3
15
107
125
52
3
NA
NA
NA
53
4
3
18
110
131
12
54
5
3
16
108
127
12
55
6
3
18
106
127
12
0
3
4
116
123
0
57
1
NA
NA
NA
58
2
3
16
110
129
11
59
3
3
17
106
126
11
60
4
3
17
106
126
12
61
5
NA
NA
NA
62
6
3
21
104
129
11
0
3
5
117
125
0
64
1
2
15
108
125
7
65
2
3
17
107
127
12
66
3
3
19
105
127
7
67
4
3
20
103
126
12
68
5
3
20
103
126
15
69
6
3
18
108
129
8
Dried Not
1
60
90
63
1
Κ
50
56
2
Na
under
vacuum.
analyzed.
2
7 12
4
11
322
GEOCHEMICAL PROCESSES AT MINERAL SURFACES
100
days.
shaken
Phlogopite,
with
after
WD
i l l i t e
experiments, layers
formation
was the
systems
of
i l l i t e
for
proportion Sr-exchanges. with
about
days,
but
4%
1.0-nm
these
to
exception or
the
layers the
layers
layers
when
disappeared
these
than,
on
0.17, With
found
rate
of
the
the
i l l i t e for
systems,
1
layers
at
K-smectite
unstable
more,
i l l i t i c a
of
subsequent
were
or
final
ratio
of
layers
of
and
The
initial
number
i l l i t e
ratios
percentage illite-layer
material.
containing
formed
that
on
and
experiments
systems
significant
i l l i t i c
depended of
a The
potassium-feldspar
system,
ratio
the
cycles.
contained
Sr-exchange.
of
greater
for
a
produced
WD
that
in
With
respect
phlogopite,
100
greatest
K-mineral/Na-Kinney
to,
formed
100
however,
after
least
the
for
Sr-exchange. All
of
however,
Na-Kinney
and
with
material
rate
(Table
and
equivalent
IX).
Conclusions The
experiments
reactions can
indicate
that
occur
rearrange
clay
substantially cations,
of
The
can
by the
to
does
environments.
WD
laboratory The
also are
in to
or From
unsaturated water
of
the
also
investigated
heterogeneous
layer-charge
ordering
the
toxic
of in
chemical
the
2:1
in
be
these
of
(67,
swelling
radioactive
than
the
Κ
process
store
it
experiments,
free
varying
tetrahedral
factors
other
such
as
three-dimensional
Finally, barriers
because
can
factors
and
the
ground
availability of
by
lake water
in
with
with angle
used
a
ancient to
and and
be
when
of the
This
plains, could
released WD
in
smectite
concentrates
the
by
typical
process.
here
influenced
wastes,
less
studied
clay,
clay
been
greatly
discover
then
(66),
in
flood
are
68).
where
has
been
drying
to
WD
on
distribution
layers
design
and
may
and
as
are
fluctuating,
and
these
subaqueous
that
deltas,
expanding
charge
in
(most
described
cations
cycles,
K-exchange
therefore,
wherever
and
Agriculturally, in
has
occur
a
a
layers
WD
affected
nature.
cores
K-minerals,
smectite-layer
WD
to
perspective,
runoff. soluble
of
Simple
reaction,
in
of
by
illite
number
not
which
soils,
important
nature
pH e n v i r o n m e n t s
by
is
reaction
other
of
temperatures
sediment
whereas
Availability
those
considered
the
65).
wetting
surface
geochemical
high
quickly
that
in
of
availability
on
rotation. than
a
of
example,
find
surface
depending
in
an
in
deposition
(64,
rate
or
be
smectite;
in
lakes
the
the
chemical
expected to
to
in
found
abundantly is
studies
sparingly
degrees
Κ
may
smectite. to
WD b y
Thus,
patterns
zone,
and
from
occur
for
geologically
is
WD
percentage
layers
compositions
of
the
was
Κ
can
exchange
K-minerals
The
reaction
subjected
Thus,
table.
on
process
competing
temperatures
relatively
the
may
fixation
dry,
effect
This
configurations,
for
that
prior
alkaline
form
and
occurs,
playas.
major
low
original
WD
environments.
K-minerals process
stable
proportional the
without
for
solution
near-surface
is
by
form
layers
in
(56)·
exception
may
cycles),
at
i l l i t e
form
previously
changes
indicate
of
stable
The
layers
Illite 20
more
a
interface.
selectivity
I/S
charge
produce
reported
have
sparingly-soluble
also
mechanism
layer
probably
i l l i t e
into
weather
mechanism
this
not
layers
layers
producing
transformation formed
can
smectite. for
and
WD
mineral-water
smectite
experiments
mechanism
that
the
2:1
alter
and
presence
at
WD used
the
should to
process
be
contain could
EBERL ET AL.
14.
Table to
IX.
Percentage
100 W e t t i n g
Mineral
at
Potassium
60
and
of
Fixation
I l l i t e
Drying
in
Layers
Cycles
in
323
Smectite
Found
the
in Na-Kinney
Presence
of
Ratio Number
70
Potassium Mineral
Microcline
71 72 73
Muscovite
74 75 76
Glauconite
77 78
Phlogopite
79 80 81
Not
I l l i t i c material
analyzed.
Subjected
Potassium
°C
I l l i t e
Reference
a
of
weight
K-Minera1 Weight
No
layers
Sr-exchange
(7o)
1 Sr-exchange
to
Na-Kinney
0.17
1
9
1.00
NA
i
0 43 40
5.00
48
0.17
25
0
1.00
NA
37 NA
5.00
47
0.17
30
0
1.00
NA
37
0.17
28
0
1.00
NA
31
0.17
30
0
1.00
NA
24
GEOCHEMICAL PROCESSES AT MINERAL SURFACES
324
cause
barriers
absorptive
to
crack,
or,
at
least,
to
lose
some
of
D.
Morgan,
their
properties.
Acknowledgments We
thank
C.
V.
Smithsonian help
of
cycles isotope original
Eric is
Clemency,
Institution Stenzel
i n
appreciated.
analyses.
improvement. penetrating
V. A.
and Drits
comments.
for
supporting
was
carried out.
Grim,
J . Hower,
supplying
conducting Rigel
Gene
manuscript
R. for
numerous
Lustwerk
Whitney offered reviewed
J a n Srodon
him as a v i s i t i n g
samples.
and
ran Len
helpful a later thanks
exchange
wetting many
of
Schultz
patient
and
drying
the
oxygen
reviewed
suggestions version
and the
The
for
and offered
the U.S. Geological scientist
while
this
the i t s many
Survey study
Literature Cited 1. 2. 3. 4. 5. 6. 7. 8. 9. 10. 11. 12. 13. 14. 15. 16. 17. 18. 19. 20. 21. 22. 23. 24. 25. 26. 27. 28. 29.
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