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
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
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
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 )
99
98
97
-1 0 -5 0 5 10
V e lo c ity ( m m /s )
* 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
* 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
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 )
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 )
? ?
“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.