57 Fe Mössbauer Spectroscopy :

a Tool for the Remote Characterization of

Phyllosilicates?

Enver Murad
Marktredwitz, Germany
 Basic principles of
Mössbauer 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

2
E γ
γ-ray energy
Energy of recoil ER = 2
2mc 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

2
E
 
 

Mössbauer spectroscopy is the γrecoil-free emission

R E =
and absorption of gamma rays 2
 
2Mc Mass of particle
 Appearance of Mössbauer spectra
Depending on the local environments of the Fe atoms and the
magnetic properties, Mössbauer spectra of iron oxides can consist of a
singlet, a doublet, or a sextet.

Magnetic hyperfine field

Quadrupole splitting
Isomer shift

δ Δ Bhf
Symmetric charge Asymmetric charge Symmetric or asymmetric charge
No magnetic field No magnetic field Magnetic field (internal or external)
R e la t iv e T r a n s m is s io n

Fe3+ Fe2+
δ
-4 -2 0 2 4
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 0 5 10
V e lo c ity ( m m /s )
Use of Mössbauer 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
Mössbauer
parameters can
therefore be used to
“fingerprint” an
unknown phase.
Hyperfine parameters of Fe3+ oxides
Ordering Magnetic hyperfine fields
Mineral
temperature (K) RT: Bhf (T) 4.2 K: Bhf (T) Δ (mm/s)
Hematite ≤ 950 ≤ 51.8 ≤ 53.5 -0.20 / 54.2 +0.41
Magnetite ≤ 850 ≤ 49.2 + 46.1 ≤ 50.6 { + 36 – 52 } #
Maghemite ≤ ~ 950 ≤ 50.0 + 50.0 ≤ 52.0 + 53.0 ≤|0.02|
Goethite ≤ 400 ≤ 38.0 ≤ 50.6 -0.25
Akaganéite ≤ 299 – ≤ 47.3 + 47.8 + 48.9
Lepidocrocite ≤ 77 – ≤ 45.8 0.02
Feroxyhyte ≤ 450 ≤ 41 ≤ 53 + 52 ~0.0
Ferrihydrite 25 – 115 * – 47 – 50 -0.02 – -0.07
Bernalite ≤ 427 ≤ 41.5 ≤ 56.2 ≤|0.01|

* Magnetic blocking temperature # several B-site subspectra below 120 K

Iron in phyllosilicates
 O
1:1 phyllosilicates
Fe3+ Si

O H ,O

Fe2+, Fe3+ Al

Si
2:1 phyllosilicates
Fe3+

Al
Fe2+, Fe3+
O H
Si

O
Classification of clay-sized phyllosilicates
(clay minerals sensu stricto)
Octahedral Octahedral Central
Layer type Group Common species
occupancy charge 1 cation(s)
1:1 Di 2 0 Al, (Fe) Kaolin Kaolinite, halloysite

1:1 Tri 3 0 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

Mössbauer spectra of selected
“simple” (pure) clay minerals
 The “simplest” clay mineral:
100

kaolinite [Al2Si2O5(OH)4]
9 9 .5
T r a n s m is s io n ( % )

O
99

Si
9 8 .5

O H ,O
98

Al
-7 .5 -5 -2 .5 0 2 .5 5 7 .5
V e lo c ity ( m m /s )

Kaolin / Jari @ 295 K

 100
T r a n s m is s io n ( % )

99

98

97

-1 0 -5 0 5 10
V e lo c ity ( m m /s )

Kaolin / Jari @ 4.2 K

 Mössbauer parameters of clay minerals

Isomer shift Quadruple

Mineral Temp
(δ/Fe) splitting (Δ)

Kaolinite RT 0.35 * 0.51*

* Average values. Isomer shift relative to α-Fe at room temperature. Only Fe3+ considered.
Illite: (K,H3O)x+y(Al2-xMx)(Si4-yAly)O10(OH)2
100

T r a n sTmr ai sn ss i om n i s ( s%i o ) n ( % )
99
Fe3+: 2 Δ
98

97
100
96
99
95
Fe3 3+: P(Δ) 6
9 8 -6 -3 0

97

96

95
-6 -3 0 3 6
16

12
(% )

8
P

0
0 0 .2 5 0 .5 0 .7 5 1 1 .2 5 1 .5 1 .7 5 2 2 .2 5
 (m m /s ) Illite OECD #5
Mössbauer parameters of clay minerals

Isomer shift Quadruple

Mineral Temp
(δ/Fe) splitting (Δ)
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
100
23.46 % Fe
RT
T r a n s m T i rs as ni os nm (i s% s )i o n ( % )

90

80

70
100
-1 0 -5 0 5 10 1.44 % Fed
V e lo c ity ( m m /s ) 77 K
95 → 2.3 % Gt
90 From Asext
85
→ 1.4 % Gt
-1 0 -5 0 5 10
V e lo c ity ( m m /s )
Nontronite API H33a
Nontronite: MxFe3+
2 (Si4-xFex)O10(OH)2

100 Fe2+/(Fe2++Fe3+) = 0.15

DCB
98
T ra n s m is s io n (% )

96

100

98
-4 -2 0 2 4 Reoxidized 644 days
V e lo c it y ( m m / s )
96 in air → no Fe2+
94

92
-4 -2 0 2 4
V e lo c ity ( m m /s )

Nontronite API H33a

Mössbauer parameters of clay minerals

Isomer shift Quadruple

Mineral Temp
(δ/Fe) splitting (Δ)
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
“Nature’s trashcan”
Mössbauer 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 −0.11 % goethite

-1 0 -5 0 5 10
V e lo c ity ( m m /s )
Kaolin “Wolfka” @ 4.2 K
 100

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 ( % )

98

B X -N
96

100
-1 0 -5 0 5 10
V e lo c ity ( m m /s )

99

3 x D C B 295 K
98 Bauxite
-1 0 -5 0 5 10
V e lo c ity ( m m /s )
 100

98
295 K

96

94

92
120 K
T r a n s m is s io n ( % )

100

98

96 77 K
100

98

96 4 .2 K
100

98

96 Red soil
-1 0 -5 0 5 10
V e lo c it y ( m m / s )
 Extraterrestrial Mössbauer
spectroscopy

 Lunar samples
 In situ Mössbauer 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

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

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

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

-5 0 5
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
“… data shouldthe
we assign notbroad
... bedoublet
interpreted in aninisolated
present Mössbauer form,
but ... correlated
spectra with
of [Mars] thetoresults
soils be dueofto
other
Fe 2+techniques
sulfates ...”
rather
NASA/JPL/University of Mainz
(S.S.
thanHafner
olivine1975)
… ” (Bishop et al. 2004)
Summar y
 Strengths and weaknesses of 57Fe
Mössbauer spectroscopy
Strengths Weaknesses
• Sensitive only to 57Fe • Sensitive only to 57Fe
(no matrix effects) (“sees” only 57Fe)
• Sensitive to oxidation state • Coordination ? to ±
• Allows distinction of • Paramagnetic phase data
magnetic phases often ambiguous
• Very sensitive towards • Diamagnetic element
magnetic phases substitution & relaxation
• Non-destructive • Slow
• Resolution limited by • If possible, use other
uncertainty principle techniques as well
Often a combination of Mössbauer spectroscopy with
other techniques can help solve problems that cannot
be resolved using Mössbauer spectroscopy alone.