57

Fe Mssbauer Spectroscopy :

a Tool for the Remote Characterization of

Phyllosilicates?

Enver Murad
Marktredwitz, Germany

Basic principles of
Mssbauer spectroscopy

Free emitting and absorbing atoms

E m is s io n

A b s o r p tio n

R e c o il

-ray energy
Energy of recoil
Mass of atom

Emitting and absorbing atoms fixed in a lattice

E m is s io n

A b s o r p tio n

N o r e c o il

Mssbauer spectroscopy is the recoil-free emission

and absorption of gamma rays
Mass of particle

Appearance of Mssbauer spectra

Symmetric charge
No magnetic field

Asymmetric charge
No magnetic field

Bhf

Magnetic hyperfine field

Quadrupole splitting

Isomer shift

Depending on the local environments of the Fe atoms and the

magnetic properties, Mssbauer spectra of iron oxides can consist of a
singlet, a doublet, or a sextet.

Symmetric or asymmetric charge

Magnetic field (internal or external)

R e la tiv e T r a n s m is s io n

Fe3+

Fe2+

-4

-2

V e lo c ity ( m m /s )

T r a n s m is s io n

0 . 4 1 m m / s
[ 0 . 0 0 m m / s ]
-1 0

-5

V e lo c ity ( m m /s )

10

Use of Mssbauer spectroscopy as a

fingerprinting technique
Isomer shifts and
quadrupole splittings
of Fe-bearing phases
vary systematically
as a function of Fe
oxidation, Fe spin
states, and Fe
coordination.
Knowledge of the
Mssbauer
parameters can
therefore be used to
fingerprint an
unknown phase.

Hyperfine parameters of Fe3+ oxides

Mineral
Hematite

Ordering
temperature (K)

Magnetite
Maghemite
Goethite
Akaganite

Ferrihydrite
Bernalite

950

850
~ 950

51.8

53.5 -0.20 / 54.2 +0.41

#

49.2 + 46.1 50.6 { + 36 52 }

50.0 + 50.0 52.0 + 53.0 |0.02|
50.6 -0.25
38.0

400
299

Lepidocrocite 77
Feroxyhyte
450

Magnetic hyperfine fields

RT: Bhf (T) 4.2 K: Bhf (T) (mm/s)

47.3 + 47.8 + 48.9

25 115

427

* Magnetic blocking temperature

45.8

41

53 + 52 ~0.0

47 50 -0.02 -0.07

41.5
# several

0.02

56.2 |0.01|

B-site subspectra below 120 K

Iron in phyllosilicates

Fe3+

1:1 phyllosilicates

Si
O H ,O

Fe2+, Fe3+

Al

Fe2+,

2:1 phyllosilicates

Si

Fe3+
Al

Fe3+

O H
Si
O

Classification of clay-sized phyllosilicates

(clay minerals sensu stricto)
Layer type

Octahedral
occupancy

Octahedral
charge 1

Central
cation(s)

Group

Common species

1:1

Di 2

Al, (Fe)

Kaolin

Kaolinite, halloysite

1:1

Tri 3

Mg, (Fe)

Serpentine

Lizardite, chrysotile

2:1

Di

< 0.2

Al, (Fe)

Pyrophyllite

Pyrophyllite

2:1

Tri

< 0.2

Mg, (Fe)

Talc

Talc, minnesotaite

2:1

Di / Tri

0.2 0.6

Al, Mg, Fe

Smectite

Montmorillonite, nontronite

2:1

Di / Tri

0.6 0.9

Al, Mg, Fe

Vermiculite

Vermiculite

2:1

Di / Tri

> 0.9

Al, Mg, Fe

Mica

Illite, glauconite

2 : 1 (: 1)

Di / Tri

Al, Mg, Fe

Chlorite

Clinochlore, chamosite

1 Per

formula unit [O10(OH)2], 2/3 Dioctahedral/Trioctahedral

Mssbauer spectra of selected

simple (pure) clay minerals

The simplest clay mineral:

kaolinite [Al2Si2O5(OH)4]
100

T r a n s m is s io n ( % )

9 9 .5

99

Si
9 8 .5

O H ,O
98

Al
-7 .5

-5

-2 .5

V e lo c ity ( m m /s )

2 .5

7 .5

Kaolin / Jari @ 295 K

T r a n s m is s io n ( % )

100

99

98

97
-1 0

-5

V e lo c ity ( m m /s )

10

Kaolin / Jari @ 4.2 K

Mssbauer parameters of clay minerals

Mineral

Temp

Isomer shift Quadruple

(/Fe)
splitting ()

Kaolinite

RT

0.35 *

0.51*

* Average values. Isomer shift relative to Fe at room temperature. Only Fe3+ considered.

Illite: (K,H3O)x+y(Al2-xMx)(Si4-yAly)O10(OH)2
T r a n sTmr ai sn ss i om n i s ( s%i o ) n ( % )

100
99

Fe3+: 2

98
97
100
96
99 95
9 8 -6

-3

-3

Fe3 3+: P() 6

97
96
95

P (% )

16

-6

12
8
4
0
0

0 .2 5

0 .5

0 .7 5

1 .2 5

(m m /s )

1 .5

1 .7 5

2 .2 5

Illite OECD #5

Mssbauer parameters of clay minerals

Mineral

Temp

Isomer shift Quadruple

(/Fe)
splitting ()

Kaolinite

RT

0.35

0.51

Illite

RT

0.35

0.59 0.73 *

* Average values for Fe-poor ( 3% Fe) and Fe-rich (> 5% Fe) samples, respectively

Nontronite: MxFe3+
2 (Si4-xFex)O10(OH)2
T r a n s m T i rs as ni os nm (i s% s )i o n ( % )

100

RT

23.46 % Fe

90

80

70
100
-1 0

-5

95

V e lo c ity ( m m /s )

10

77 K

1.44 % Fed
2.3 % Gt
From Asext
1.4 % Gt

90
85
-1 0

-5

V e lo c ity ( m m /s )

10

Nontronite API H33a

Nontronite: MxFe3+
2 (Si4-xFex)O10(OH)2
Fe2+/(Fe2++Fe3+) = 0.15

100

DCB
T r a n s m is s io n ( % )

98

96
100
98

-4

-2

-4

-2

96

V e lo c it y ( m m / s )

Reoxidized 644 days

in air no Fe2+

94
92

V e lo c ity ( m m /s )

Nontronite API H33a

Mssbauer parameters of clay minerals

Mineral

Temp

Isomer shift Quadruple

(/Fe)
splitting ()

Kaolinite

RT

0.35

0.51

Illite

RT

0.35

0.59 0.73

Nontronite

RT

0.35

0.35

Complex natural clays :

The real world

Na+
H2O

CH4
Fe3+

Fe2+

Phyllosilicate
Note:
Fe-containing
with intercalated
interlayer must
interlayer
interlayer:
be
frozen to show
Natures
trashcan
Mssbauer Effect

Physics Today 61 (8)

1 0 0 .0

T ra n s m is s io n (% )

9 9 .8
9 9 .6

1 0 0 .0
9 9 .8
9 9 .6
DCB-treated

-1 0

-5

0.11 % goethite

V e lo c ity ( m m /s )

10

Kaolin Wolfka @ 4.2 K

T r a n s m i t t a n c e ( %T r )a n s m i s s i o n ( % )

100

98

B X -N
96
100

-1 0

-5

V e lo c ity ( m m /s )

10

99

295 K

3 x D C B

98
-1 0

-5

V e lo c ity ( m m /s )

10

Bauxite

100
98

295 K

96
94

T r a n s m is s io n ( % )

92
100

120 K

98
96
100

77 K

98
96
100

4 .2 K

98

Red soil

96
-1 0

-5

V e lo c it y ( m m / s )

10

Extraterrestrial Mssbauer
spectroscopy
Lunar samples
In situ Mssbauer spectroscopy on Mars

Lunar soil 10084

N a n o p h a s e ir o n

M e ta llic ir o n

R e s o n a n t a b s o r p tio n

F e 2 + in o liv in e
F e 2 + in ilm e n ite
F e 2 + in p y r o x e n e
F e 2 + in g la s s

W a n g e t a l., 1 9 9 5
-5

0
V e lo c ity ( m m /s )

S.S. Hafner, 1975: The data should not ... be interpreted

in an isolated form, but ... correlated with the results of
other techniques .... For lunar samples, this is possible !

 Fe2+ sulfate ?

The
shouldthe
notbroad
... bedoublet
interpreted
in aninisolated
form,
data
we assign
present
Mssbauer
but
... correlated
with
thetoresults
other
2+techniques
...
spectra
of [Mars]
soils
be dueofto
Fe
sulfates
rather
NASA/JPL/University of Mainz
(S.S.
thanHafner
olivine1975)
(Bishop et al. 2004)

Summar y

Strengths and weaknesses of 57Fe

Mssbauer spectroscopy
Strengths
Sensitive only to 57Fe
(no matrix effects)
Sensitive to oxidation state
Allows distinction of
magnetic phases
Very sensitive towards
magnetic phases
Non-destructive
Resolution limited by
uncertainty principle

Weaknesses
Sensitive only to 57Fe
(sees only 57Fe)
Coordination ? to
Paramagnetic phase data
often ambiguous
Diamagnetic element
substitution & relaxation
Slow
If possible, use other
techniques as well

Often a combination of Mssbauer spectroscopy with

other techniques can help solve problems that cannot
be resolved using Mssbauer spectroscopy alone.