Potassium Fixation in Smectite by Wetting and Drying - American

and Na-Black. Jack smectite are given in Figure 1. A. Na-K exchange isotherm was determined using. Na-Kinney smectite to study the evolution of 3-comp...
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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)



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 =



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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