Annual Review of Earth and Planetary Sciences Volume 34 Issue 1 2006 Dyar, M. Grant, C MÖSSBAUER SPECTR PDF

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Mossbauer
Spectroscopy of Earth
and Planetary Materials
M. Darby Dyar,1,2 David G. Agresti,3 Martha W. Schaefer,4
Christopher A. Grant,5 and Elizabeth C. Sklute2
1
Department of Earth and Environment and 2 Department of Astronomy, Mount Holyoke College,
South Hadley, Massachusetts 01075-1429; email: mdyar@mtholyoke.edu, ecsklute@mtholyoke.edu
Department of Physics, University of Alabama at Birmingham, Birmingham, Alabama 35294-1170;

email: agresti@uab.edu
Department of Geology and Geophysics, Louisiana State University, Baton Rouge, Louisiana 70803;
email: schaefer@geol.lsu.edu
Annu. Rev. Earth Planet. Sci.

2006. 34:83125
First published online as a
Review in Advance on
January 16, 2006
The Annual Review of
Earth and Planetary Science
is online at
earth.annualreviews.org
doi: 10.1146/
annurev.earth.34.031405.125049
c 2006 by
Copyright
Annual Reviews. All rights
reserved
0084-6597/06/05300083$20.00
Department of Chemistry, University of Oregon, Eugene, Oregon 97401
Key Words
resonant absorption, recoil-free fraction, iron valence state, iron
site occupancy, quadrupole splitting distribution
Abstract
The eld of Mossbauer

spectroscopy (MS) has recently enjoyed renewed visibil
ity in the diverse geoscience communities as a result of the inclusion of Mossbauer
spectrometers on the Mars Exploration Rovers. Furthermore, new improvements
in technology have made possible studies involving very small samples (15 mg or
less) and samples with very low Fe contents (such as feldspars), in addition to sam
ples measured in situ in thin sections. Because of these advances, use of Mossbauer
spectroscopy in Earth science applications is expected to continue to grow, providing
information on site occupancies; valence states; magnetic properties; and size distributions of (largely) Fe-bearing geological materials, including minerals, glasses, and
rocks. Thus, it is timely to review here the underlying physics behind the technique,
with a focus on the study of geological samples. With this background, recent advances in the eld, including (a) changes in instrumentation that have allowed analysis
of very small samples and of surface properties, (b) new models for tting and interpreting spectra, and (c) new calculations of recoil-free fraction, are discussed. These
results have made possible increasingly sophisticated studies of minerals, which are
summarized here and organized by major mineral groups. They are also facilitating
processing and interpretation of data from Mars.
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INTRODUCTION
MS: Mossbauer
spectroscopy
XPS: X-ray photoelectron
spectroscopy
EELS: electron-energy loss
spectroscopy

XANES: X-ray absorption

near-edge spectroscopy
Mossbauer
effect:
emission or absorption of a
gamma photon without
energy loss (or gain) in a
transition between the
ground state and an excited
state of certain nuclei bound
in a solid
84
The technique of Mossbauer

spectroscopy (MS) has long shared with wet chemistry
the distinction of being a gold standard for determinations of Fe3+ and Fe2+ in
solid materials, including a host of geological materials. The primary limitation of
both techniques has traditionally been their need for signicant masses of powdered
samples, a restriction that has conned their usefulness to large samples and made
difcult the study of rock-forming minerals within many important rock types for
which obtaining large, pure mineral separates may be difcult.
For smaller samples, alternative techniques have been developed for Fe3+ /Fe2+
measurements, but each has its own problems. Many workers have attempted to use
electron microprobe analyses to calculate Fe3+ and Fe2+ on the basis of charge balance, but repeated studies have shown that this is limited to specic mineral groups,
such as spinels (Wood & Virgo 1989), or impractical, especially for silicates (Canil
& ONeill 1996, Dyar et al. 1989, Sobolev et al. 1999). In optical spectroscopy,
Fe3+ peaks may be difcult to quantify because orientation must be controlled, the
peaks lie at low energies near the UV, and electronic interactions among species
can complicate interpretations. The inherent anisotropy of the majority of minerals
also adds uncertainty to other promising techniques for measurement of Fe3+ and
Fe2+ by other microbeam methods, such as X-ray photoelectron spectroscopy (XPS)
(Nesbitt et al. 2004), electron-energy loss spectroscopy (EELS) (Garvie et al. 2004),
and synchrotron X-ray absorption near-edge spectroscopy (XANES) (Dyar et al.
2002a). Milliprobe Mossbauer

measurements have also found wide application (McCammon 1994, Sobolev et al. 1999). Despite these recent advances, the dominant
technique for measuring Fe3+ and Fe2+ in geological materials remains conventional
Mossbauer
spectroscopy on powdered samples.
Papers describing the use of MS in mineralogy rst appeared in the early 1960s
(Pollak et al. 1962, de Coster et al. 1963), followed by a systematic investigation of
common rock-forming minerals by Bancroft and Burns within 10 years of Mossbauers

original discovery (e.g., Bancroft 1967, 1969; Bancroft & Burns 1967, 1969; Bancroft
et al. 1967a,b,c, 1971; Bancroft & Brown 1975). Use of the technique continues
to grow, with generally more than 100 studies of the Mossbauer

effect in minerals
published each year since the 1970s. Most recently, application of the technique
has moved from the realm of pioneering mineralogical characterization to routine
application to a steady stream of geological problems, moving from spectroscopy
into geoscience. For the latter community, we have long recommended Bancrofts
(1973) seminal book, Mossbauer Spectroscopy: An Introduction for Inorganic Chemists and
Geochemists, for geologically applied background information on the technique, but
that publication is getting rather out of date.
Thus, the goal of this review is to create an accessible summary of the Mossbauer
technique in its current implementation, to inform students and collaborators, to
introduce new users to its capabilities, and to generally advance and advocate for this
area of research. Accordingly, four major sections are included: a summary of the
physics behind the Mossbauer

effect, how it is applied to mineralogical studies, how
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current instrumentation and data processing are accomplished, and a brief overview
of new directions for the technique.
HOW THE MOSSBAUER

EFFECT WORKS

Fundamentals of Resonant Absorption
Recoilless nuclear resonance was discovered by Mossbauer

during his graduate studies at Heidelberg in 1957. It relies on the principle of resonant absorption of nuclear gamma rays in solids. Early discussions of the technique appear in Frauenfelder
(1962), who summarizes important early developments and provides reprints of major
early works, and Wegener (1965), who provides a thorough grounding in the theory
of the spectroscopy.
Many geoscientists are already familiar with the concept of resonant absorption
from the perspective of electronic events. When the energies of 3d orbitals in transition metals are split, it becomes possible for electrons to undergo a transition between
orbitals when energy is added. This is one of the most common causes of colors in
minerals. Only very specic energies (wavelengths) of light can lead to such resonant
absorption phenomena.
An analogous process occurs with the addition or loss of energy to the energy levels
in the nucleus. An isolated atom in an excited nuclear state Ee (such as a radioactive
isotope) will decay and give off a gamma ray or transfer the transition energy to an
atomic electron. If we assume for simplicity that the departing gamma photon carries
away the entire energy (E0 ; Figure 1, top), and the gamma photon then impinges
on another, identical atom, it can be absorbed by resonant capture. The absorber
nucleus may then deexcite by emitting another gamma photon (Figure 1, bottom).
As for atomic electrons, resonance absorption requires that the photon have exactly
the correct quantized transition energy.
However, the excited state has a nite lifetime, . According to the Heisenberg
uncertainty principle, the energy of the emitted gamma ray is then not precisely
dened, but rather obeys a Breit-Wigner, or Lorentzian, distribution (Figure 1,
top), centered on E0 with full width at half maximum, 0 , given by 0 = h/
, where
h is Plancks constant divided by 2.
The previous model assumes that the departing gamma photon carries away the
entire energy of the nuclear transition, i.e., E = E0 . In fact, the photon has momentum, p = E /c , where c is the speed of light. If we assume the emitting atom
is isolated and initially at rest, then conservation of momentum dictates that it must
recoil with momentum, pnucleus = p , and acquire a recoil energy, ER , given by
ER =
E2
( p nuc leus )2
( p )2
=
=
,
2M
2M
2Mc 2
Resonant absorption:
absorption of a photon
whose energy is precisely
matched to that of a
transition in the absorbing
medium
(1)
where M is the mass of the emitting nucleus. By conservation of energy, the transition
energy is then shared between the nuclear recoil and the emitted photon, whose
energy is thus reduced to E = E0 ER . Similarly, a photon that can be absorbed
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Figure 1
Idealized representation
of the process of nuclear
resonance uorescence.
The source in an excited
nuclear state decays and,
in a rst-excited- to
ground-state transition
(top), gives off a gamma
photon with an energy
that obeys a Breit-Wigner,
or Lorentzian,
distribution centered on
E0 . When the gamma
photon impinges on
another absorber atom
(bottom), it can be
absorbed by resonant
capture, subsequently
emitting a gamma photon
of the same energy as the
nucleus returns to its
ground state.
Ee
0 = h / = FWHM
emission
lifetime,
Eg
N( )
E0
E0
Source nucleus
Ee
absorption
Ee
reemission
Eg
E( )
Eg
Absorber nucleus
by an isolated atom at rest in a nuclear transition of energy E0 must possess an

additional energy, ER , to allow for the nuclear recoil. Thus, to be resonantly absorbed,
E = E0 + E R .
Although the recoil energy (104 101 eV for free atoms) (Greenwood & Gibb
1971) is considerably smaller than the gamma energy (104 105 eV), it is still so large
relative to the gamma energy distribution represented by the linewidth shown in
Figure 1 (109 106 eV) that a nuclear resonant emission-absorption process cannot
occur between free atoms at rest.
On the other hand, if the emitting nucleus were moving toward the absorbing
nucleus with a relative velocity, v, the energy of the emitted gamma photon would be
Doppler shifted by an amount,
E = E (v/c ).
(2)
In principle, the resonance process could occur if v were sufciently large (4

4000 m/s) that E = 2 ER , for then the emitted photon would have energy E =
E0 + E R , precisely what is required for absorption. However, this is highly impractical
because of the extreme narrowness of the photon distribution relative to ER and the
large velocities that would have to be produced with very high accuracy.
In reality, atoms are found in gases, liquids, or solids, and thus exhibit thermal motion with kinetic energy on the order of k B T, where k B is Boltzmanns constant and T
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is the absolute temperature. At room temperature, T 300 K and k B T 0.025 eV,

on the order of magnitude of E R . By the Doppler effect, a comparable amount of
energy is either added to, or subtracted from, an emitted gamma photon, depending on the direction of motion of the emitting nucleus, and a thermally broadened
distribution of emitted photon energies is the result. A similar circumstance applies
with respect to the energy required for resonant absorption. Thus, the nuclear recoil
may be partially compensated by thermal motion and a certain amount of resonant
absorption may occur.
The preceding argument suggests that as temperature is lowered, the thermally
broadened distributions become narrower and absorption is reduced, eventually to
zero at the lowest temperatures. This is what Mossbauer

initially observed in his
experiments, but as the temperature approached that of liquid nitrogen, contrary to
expectations, the absorption increased dramatically (Mossbauer

1958). The explana
tion for this phenomenon, the Mossbauer
effect, is not to be found in the foregoing
discussion but rather in the quantized nature of the vibrational spectrum of a solid.
Because a correct theoretical treatment (e.g., Mossbauer

1958, Visscher 1960) is beyond the scope of this work, we illustrate here the principal ideas by means of a highly
simplied model.
A solid (with harmonic interatomic forces) may be regarded as consisting of a large
number (three times the number of atoms) of vibrational modes, each one involving,
in principle, all the atoms of the solid. In the Debye model, there is a distribution
of vibrational frequencies. In the simple Einstein model, which we assume for now,
each mode has a single characteristic vibrational frequency, . The energy of each
simple harmonic mode is then quantized such that
E SH M = (n + 1/2 ) h,
Zero-phonon transition
(recoil-free transition):
nuclear transition in which
the host lattice does not
change its vibrational state,
so that the emitted or
absorbed gamma photon
carries the full transition
energy. This is the basis for
the Mossbauer
effect
(3)
where n = 0, 1, 2, . . . is the vibrational quantum number, or the number of phonons

associated with the energy state. In emission or absorption of a gamma photon by a
nucleus, n (the phonon number) may or may not change (increase or decrease). If it
stays the same, the photon is absorbed in a zero-phonon process because no phonons
are created (n does not increase) or destroyed (n does not decrease).
When a photon is emitted or absorbed by a nucleus, the solid takes up or releases
vibrational energy (n may change); the precise amount is predicted from a probability
distribution. In a theoretical work remarkable for its simplicity and insight, Lipkin
(1960) showed that the energy imparted to a crystal, averaged over a large number of
emitted gammas, is exactly equal to the recoil energy, E R .
We now apply the simplifying assumption of an Einstein model, that is, there is
only one frequency, . Let us assume that E R < h
(Figure 2a) and that, during the
emission of a gamma photon, n either stays the same or increases by exactly 1, i.e.,
the solid undergoes a zero- or a one-phonon transition. (In a zero-phonon transition,
the recoil momentum is picked up by the entire solid and, because of its large mass,
M, according to Equation 1, the recoil energy is negligible.) Dene the symbol f to
be the fraction of zero-phonon transitions, known also as the recoil-free fraction.
Then the average energy given to the crystal is (1-f ) h.
Thus, according to Lipkin
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h w
En+1
ER
En+1
ER
En
En
Figure 2
Vibrational energy levels in a solid (schematic). (a) The recoil energy ER of an emitted gamma
photon is less than that required to reach the next higher energy level, so that excitation of a
vibrational mode has low probability. The probability that no excitation will occur is given the
symbol f, which represents the fraction of recoil-free events. Thus, a gamma ray would be
emitted without losing energy to the solid in a zero-phonon transition. This forms the basis
for Mossbauer
spectroscopy. (b) ER is signicantly greater in energy than the lowest excitation
energy of the solid (En+1 En ). Absorption of the recoil energy, E R , by the solid thus
becomes probable, and the photon emerges with energy reduced by E R and with Doppler
broadening. Adapted from May (1971).
(1960), E R = (1 f ) h,
and in turn (in this simple model),
f = 1 E R /h.
(4)
this simple model fails, but then zero-phonon transitions also become
For E R > h
much less likely (Figure 2b).
Clearly, larger values of f are desirable. Thus, the Mossbauer

effect (zero-phonon
transition) is enhanced for smaller ER , or, according to Equation 1, smaller gamma
photon energies. We also see from Equation 4 that larger values of h
are desirable,
which correspond to larger Debye temperatures.
More generally, and independently of the particular vibrational model of the solid,
it can be shown (Frauenfelder 1962, equation 56) that

f = exp x 2 E2 (hc
)2 ,
(5)
where x is the component of nuclear displacement from its equilibrium position in
the direction of the emitted (or absorbed) gamma photon, and x2 is known as the
mean-squared displacement (MSD) or the mean-square vibrational amplitude. From
Equation 5, it is evident that there is also temperature dependence for f because higher
temperatures lead to larger x2 or, equivalently, larger values of n and a corresponding
higher probability that n will change, hence smaller values for f .
Finally, the Mossbauer

effect cannot occur in gases or liquids (other than highly
viscous ones) because for them translational motion is also possible, in which case
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the quantum states are so closely spaced that E R is always very much greater than the
spacing between energy levels, and f = 0.

Mossbauer
Spectroscopy of 57 Fe
What is it that makes 57 Fe special? In principle, the Mossbauer

effect applies to
any and all nuclides, but in practice, certain ideal properties are desirable; that is,
the conditions for recoil-free emission and absorption of gamma rays must be optimized. Most importantly, as seen in Equations 4 and 5, the energy of the nuclear transition must be small enough to yield a large recoil-free fraction, f . In
other words, a large fraction of nuclear transitions must be zero-phonon transitions. The lifetime of the excited nuclear state, which determines the linewidth,
should be neither too long (resulting in undue sensitivity to vibration) nor too short
(resulting in loss of resolution). A parent of sufcient half-life must exist that can
populate the excited nuclear states in a selected nuclide. Finally, the Mossbauer
isotope must have sufcient natural abundance that meaningful experiments can be
accomplished. The vast majority of Mossbauer

studies use 57 Fe, although the effect has been exploited in numerous other isotopes including 119 Sn, 61 Ni, 195 Pt, and
197
Au.
Fe is the most commonly occurring multivalent element in the terrestrial planets,
which makes it particularly important for geological studies. Although only 2.2%
of natural Fe atoms are the 57 Fe isotope, its large f (0.651) makes high-quality
Mossbauer
measurements possible. Its parent isotope is 57 Co, which has a 270-day
half-life and decays primarily to the 136.3-keV level of 57 Fe (Figure 3) following
capture of an atomic electron. Approximately 9% of the time, deexcitation is directly
to the ground state with emission of a 136.3-keV gamma photon. Otherwise, decay
is to the 14.4-keV state and then to the ground state with a half-life of 97.7 109 s
(lifetime, = t1/2 /ln2 = 141 ns).
Of the 14.4 keV transitions, 11% result in emission of a gamma ray, whereas the
remaining 89% result in transfer of the transition energy to an atomic electron (electron conversion). A number of events can occur following electron conversion. There
is emission of the conversion electrons (K, L, M) from the atom; they carry energy,
E0 = 14.4 keV minus their binding energy. That electron can then be absorbed by
a second atom, leading to emission of a characteristic X-ray photon. Or, because the
Fe atom must undergo some electronic rearrangement to accommodate the vacancy
that results, emission of characteristic X-rays and possibly Auger electrons may occur
(Figure 3). Electrons characteristically have limited escape depths in comparison to
photons of comparable energy, but they are quite useful for studying mineral surfaces
(see DeGrave et al. 2005 for a more in-depth discussion).
Various examples of the use of electrons emitted following nuclear resonant absorption include the following:
CEMS: conversion
electron Mossbauer
spectroscopy
Conversion electron Mossbauer

spectroscopy (CEMS) uses the K, L, and M
electrons to probe the top 200300 nm of a surface, allowing depth proling
below the surface of a sample (Parellada et al. 1981, Toriyama et al. 1984, Stahl
et al. 1990).
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Non-resonant
photo electrons
Compton electrons
photons
Co
57
Emitted following
resonant absorption
conversion electrons
K 7.3 keV
L 13.6 keV
e-
Fe 136.3 keV
57
M 14.3 keV
9%
Auger electrons

91%
KLL 5.4 keV

LMM ~0.6 keV
MMM < 15 eV
14.4 keV
0
shake-off electrons
SOURCE
ABSORBER
14.4 keV -rays

x-rays, various energies
Figure 3
The nuclear decay scheme for 57 Co 57 Fe and various backscattering processes for 57 Fe that
can follow resonant absorption of an incident gamma photon, modied from DeGrave et al.
(2005).
DCEMS: depth-selective
conversion electron
Mossbauer
spectroscopy
ILEEMS: integral
low-energy electron
Mossbauer
spectroscopy
SGXEMS: simultaneous
gamma, X-ray, and electron
Mossbauer
spectroscopy
Mossbauer
spectrum: a
plot of transmitted (or
scattered) intensity versus
Doppler velocity. Dips (or
peaks) occur where the
incident photon energy
precisely matches that of a
transition in the sample
being investigated, as
determined by hyperne
interaction
90
Depth-selective conversion electron Mossbauer

spectroscopy (DCEMS) uses
the 7.3 keV K-conversion or the 13.6 keV L-conversion electrons to probe at
depths of a few nanometers (Liljequist & Ismail 1985, Liljequist et al. 1985,
Pancholi et al. 1984).
Integral low-energy electron Mossbauer

spectroscopy (ILEEMS) detects lowenergy electrons, also at a few nanometer depths, which has exciting potential
for studies of mineral surfaces (Klingelhofer

& Kankeleit 1990, Klingelhofer
&
Meisel 1990, DeGrave et al. 2005).
Simultaneous gamma, X-ray, and electron Mossbauer

spectroscopy (SGXEMS)
measured gamma rays, x-rays, conversion electrons, and Auger electrons, all at
the same time, using proportional gas ow detectors (Kamzin & Vcherashnii
2002). This technique allows the surface, subsurface, and interior of a sample
to be analyzed.
Mossbauer
Parameters
Mossbauer
parameters are derived from a Mossbauer
spectrum. So how is such a
spectrum acquired? This may be seen from Figure 4, which shows three types of
spectra: (brown) the emission spectrum (energy distribution of emitted gamma photons), Doppler modulated by moving the source, see Equation 2; (red) the absorption
spectrum (probability of resonant absorption); and (blue) the transmission spectrum,
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Intensity
Figure 4
E , observed
acquired while detecting the 14.4-keV gamma rays that pass through the absorber.
As the source velocity is varied, the emission spectrum is gradually changed from
having no overlap with the absorption spectrum, to maximal overlap, and back again
to no overlap. Where overlap is small, the count rate is large, and where overlap is
large, the count rate is small owing to resonant absorption. As we follow the evolution
of the spectrum from top to bottom in Figure 4, the transmission spectrum (blue)
is gradually traced out as the velocity is varied from a large negative value (source
moving away from the absorber), through zero, to a large positive value.
What makes Mossbauer

spectroscopy useful as an analytical tool is the fact that
the nuclear energy levels may be modied (shifted and split apart) by the nuclear
electronic environment. This is known as hyperne interaction, and the parameters
involved are products of xed nuclear and variable electronic properties. Transitions
between split levels may occur, as shown in Figure 5, resulting in generally more
complex absorption spectra than the single-line pattern of Figure 4. Iron atoms in
different local environments and those having different oxidation states absorb at
different, diagnostic energies. A typical Mossbauer

spectrum thus consists of sets of
peaks (usually doublets and sextets, Figure 5), with each set corresponding to an
To form a Mossbauer
spectrum, the source is
moved to Doppler shift the
center of the emission
spectrum (brown) from
smaller to larger energies,
relative to the center of the
absorption spectrum (red ),
whose center, the quantized
transition energy, is xed.
The level of the
transmission spectrum (blue)
at each value of velocity, v,
is determined by how much
the shifted emission
spectrum overlaps the
absorption spectrum, such
that greater overlap results
in reduced transmission
owing to resonant
absorption. The evolution
of the transmission
spectrum from large
negative (source moving
away from absorber) to
large positive values of
velocity may be followed
from the top to the bottom
rows of the gure. Figure
courtesy of E. DeGrave.
Hyperfine interaction:
interaction between the
nucleus and its surrounding
electrons, leading to
changes in the nuclear (and
electronic) energy levels on
the order of 107 108 eV.
These changes provide
information that enables
characterization of the host
material
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%Transmission
ANRV273-EA34-04
QS
IS
IS
0
IS
Relative velocity

+3/2
3/2
3/2
3/2
1/2
+1/2
-1/2
-3/2
1/2
IS
Free
no
QS
atom
1/2
IS
with QS
1/2
-1/2
+1/2
Hyperfine splitting
Figure 5
When unsplit source and absorber atoms are in different local environments, their nuclear
energy levels are different. At its simplest (blue), this appears in the transmission spectrum as a
shift of the minimum away from zero velocity; this shift is generally called isomer shift (IS).
The 1/2 and 3/2 labels represent the nuclear spin, or intrinsic angular moment, quantum
numbers, I. Interaction of the nuclear quadrupole moment with the electric eld gradient
leads to splitting of the nuclear energy levels (red ). For 57 Fe, this causes individual peaks in the
transmission spectrum to split into doublets (red ) having a quadrupole splitting of QS. When a
magnetic eld is present at the nucleus, Zeeman splitting takes place, yielding a sextet pattern
( green); in the simplest case, the areas of the lines vary in the ratio of 3:2:1:1:2:3. For the
spectrum shown, the outer lines have reduced intensity because of saturation effects. Two
additional possible transitions shown in gray at the lower right (mI = 1/2 to +3/2 and mI =
+1/2 to 3/2) do not occur owing to the selection rule, |mI | 1. Note that the lengths of the
transition arrows have been greatly shortened to allow the splittings to be seen clearly.
Isomer shift (IS): shift up

or down of nuclear levels
that results from overlap of
nuclear and s-electron
charge distributions
92
iron nucleus in a specic environment in the sample (a Fe nuclear site). Different

sets of peaks appear depending on what the Fe nucleus sees in its environment.
The nuclear environment depends on a number of factors, including the number
of electrons (Fe0 , Fe2+ , Fe3+ ), the number of coordinating anions, the symmetry of
the site, and the presence/absence of magnetic ordering (which may be temperature
dependent). Thus, a room-temperature spectrum of a given mineral may consist of a
superposition of doublets and sextets.
Generally, the local environments around Fe atoms in source and absorber are
not the same, and the absorption spectrum will not be centered on zero relative
energy. This will result in an offset from zero velocity in the transmission spectrum,
which is variously called isomer shift, chemical shift, or center shift, and is commonly
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denoted by IS or (Figure 5, blue). The shift results from a Coulombic interaction

between the nuclear and electronic charge distributions, and is strictly a function of
the s-electronic charge density at the nucleus, although this density is also affected
by shielding from p, d, and f electrons and by participation of electrons in bonding.
IS values are generally reported relative to some standard absorber, usually -Fe,
although sodium nitroprusside [Na2 Fe(CN)6 NO2H2 O], which is shifted relative to
-Fe by 0.257 mm/s, is sometimes used in older papers.
In minerals, the local point symmetry of the electronic environment at the nucleus
is rarely cubic. Then, the nuclear quadrupole moment (the effective shape of the
ellipsoid of nuclear charge distribution) interacts with the gradient of the electric
eld that arises from other charges in the crystal to split the nuclear energy levels
(Figure 5, red). This splitting is called quadrupole splitting, or electric quadrupole
splitting, and is variously denoted by QS, , or EQ . The phenomenon is very much
analogous to the splitting of 3d orbitals that occurs in transition metals as a result of
crystal eld splitting. As shown in Figure 5 (red), QS has the effect of causing the
I = 3/2 level to split into two sublevels (I is the nuclear spin quantum number of
the level). In a doublet, QS is dened as the separation between the two component
peaks, i.e., the difference of the two transition energies.
Because the 57 Fe nucleus possesses a magnetic moment, its energy levels can be
perturbed if a magnetic eld is present, as for magnetically ordered materials (e.g.,
ferrimagnetic materials such as magnetite) or if an external magnetic eld is applied,
resulting in magnetic hyperne (Zeeman) interaction. The effect is to completely
remove the degeneracy of the nuclear energy levels. They split into six different
levels (Figure 5, green), with the I = 1/2 level splitting into two and the I = 3/2
level splitting into four sublevels, which are labeled with mI , the z projection of the
nuclear spin. When transition selection rules are included (|mI | 1), as is typically
correct for minerals, the resultant Mossbauer

spectrum is a sextet. Although the
linewidths of the six lines are in principle equal, their intensities are very different. In
a randomly oriented sample, for an ideal thin absorber, the area ratios of the six lines
are in proportion to the Clebsch-Gordan coupling coefcients, namely, 3:2:1:1:2:3
(Figure 5, green). As with quadrupole splitting, the IS of the sextet is the center of
gravity of the six peaks.
For combined quadrupole and magnetic hyperne splitting, the situation is more
complex owing to mixing of states (cf. Wegener 1965). If the electric quadrupole
interaction is small (leading to small shifts in line positions, li , of the magnetic sextet
pattern, as is the case for hematite), the quadrupole shift parameter is dened as
QS = (l6 l5 ) (l2 l1 ), with peaks numbered from left to right. Although the same
symbol is used as for the quadrupole splitting, the two are identical only in special
cases because the quadrupole shift depends on the relative directions of the magnetic
eld and the principal axis of symmetry of the electric eld gradient tensor.
To determine the magnitude of the magnetic hyperne eld, Bhf , in tesla (T),
use is made of the relations E g = |g| N Bhf and Eex = |g | N Bhf , where g
is the nuclear g-factor and N is the nuclear magneton. The entire sextet pattern
is t to determine the ground-state splitting, E g , in millimeter per second, while
constraining Eex /E g = g /g = 0.5714(1). Then Bhf is computed according to
Electric quadrupole
interaction: orientation of
the nuclear quadrupole
moment (spin I 1) in a
distribution of electronic
charge lacking spherical or
cubic symmetry (electric
eld gradient = 0). This
leads to a quadrupole
splitting of (or quadrupole
shift of already split) nuclear
levels, designated QS
Magnetic hyperfine
interaction: orientation of
the nuclear magnetic
moment (spin I 1/2) in an
effective magnetic eld, Bhf ,
that arises from magnetic
order or is externally
applied. This leads to
complete removal of
degeneracy (i.e., full
splitting) of the nuclear
levels
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Bhf = Eg 8.416 T(mm/s)1 , where g = 0.181208(9) and N = 3.1525 108

eV/T = 0.65572 (mm/s)/T. [From Equation 2, 4.80766(3) 108 eV is equivalent to
1 mm/s for 57 Fe.] Values are from MEDI (Stevens 1974), with errors in parentheses.
Many common rock-forming minerals exhibit magnetic ordering at low temperatures. This has the effect on the spectra of splitting doublets into sextets or even
octets (see below) over a range of temperature, such that in the temperature regime
over which this transition occurs, doublets and hyperne patterns may appear for
the same site. Spectra taken over such a transition temperature range are typically
difcult to impossible to t, however comparison of spectra above and below the
transition temperature is very valuable in determining the crystal environment of the
iron in the sample.
Some minerals, for example, fayalite, Fe2 SiO4 (Kundig et al. 1967), exhibit not
a six-line pattern at low temperature, but an eight-line pattern. This is due to
the relaxation of the transition selection rules to allow spin-forbidden transitions
(|mI | = 2), which occurs when the orientation of the nuclear magnetic moment is
not parallel to the magnetic eld of the nucleus (Schaefer 1983a,b).

ANRV273-EA34-04
Significance of Mossbauer
Parameters
The combination of IS and quadrupole splitting parameters (along with the hyperne eld in the case of magnetically ordered phases) is usually sufcient to identify the valence state and site occupancy of Fe in a given site and individual mineral
(Figures 6 and 7). In minerals, these ranges have largely been determined empirically
from Mossbauer
spectra measured with use of spectrum-tting routines commonly
available to the geological community. Exact values of Mossbauer

parameters are difcult to predict from theory because long-range interactions in complicated mineral
structures are difcult to anticipate.
As seen in Figures 6 and 7, Fe atoms in minerals are predictably found in coordination polyhedra of appropriate size based on radius ratios. As shown in Table 1,
Fe3+ occurs primarily in 4- or 6-coordination with oxygen, whereas Fe2+ may be rarely
4- or 5-coordinated, commonly 6-coordinated, and occasionally 8-coordinated with
oxygen. Fe in 4-coordination with sulfur has subtly different parameters owing to the
effects of covalent bonding. Variations in Mossbauer

parameters that are characteristic
of each type of coordination polyhedron can be related to polyhedral site distortion;
a thoughtful discussion of this topic can be found in Burns & Solberg (1988).
Rock-forming minerals on Earth most commonly contain Fe2+ in octahedral co
ordination (c.f. Paulings Rules), and thus have very similar Mossbauer
parameters.
For example, pyroxene, amphibole, and mica spectra are all nearly indistinguishable
(Table 1). Furthermore, most minerals exhibit a range of Mossbauer

parameters as a
function of cation substitution, so the values given in Table 1 should be viewed only
as starting points! Finally, the parameters vary as a function of temperature, and the
magnitude of that variation is distinctive to each mineral composition (see further
discussion of f below). For these reasons, Mossbauer

spectroscopy is not ideally suited
to mineral identication and is typically not used for this purpose (though it has been
pressed into such service in extraterrestrial applications).
94
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23:19
Isomer shift (mm/s)
1.2
0.8
0.4
0.0
0.0
0.5
1.0
1.5
2.0
2.5
3.0
3.5
1.6
Isomer shift (mm/s)

1.6
VIII
1.2
VI
VI
0.8
0.4
VI
IV
0.0
0.0
Fe2+
Fe3+Fe2+
Fe3+
0.5
1.0
1.5
2.0
2.5
3.0
3.5
Quadrupole splitting (mm/s)

Figure 6
(Top) Room temperature isomer shift versus quadrupole splitting data for common
rock-forming minerals, taken from Table 1 and Burns & Solberg (1988). Oxides are shown in
purple; suldes, sulfates, and phosphates in orange; and silicates in green. (Bottom) Fairly
distinctive ranges occur for each valence state and site occupancy of Fe, as labeled; note that
vefold coordination would lie between 4- and 6-coordination. Between the ranges for Fe3+
and Fe2+ is a poorly dened region where 0.5 > IS > 0.9 mm/s (blue rectangle); doublets with
those parameters are generally taken to represent delocalization of electrons between adjacent
Fe3+ and Fe2+ , resulting in an averaged value of IS that can be assigned to Fe2.5+ . Because
quadrupole splitting reects site distortion, relative values of QS can be used to compare
polyhedral distortion in spectra of minerals where two sites with the same coordination
number are found; these tendencies toward regular versus distorted polyhedra are shown here.
These ranges are used to infer valence state and coordination number of Fe atoms in minerals
where they are unknown. They are best used to interpret spectral parameters from silicates;
oxides, suldes, etc., tend to have broader ranges of parameters.
95
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12
11
almandine
(garnet)
10
9
forsterite
(olivine)

% Absorption
7
6
staurolite
5
4
3
jarosite
(alunite)
2
1
0
-1
glauconite
(mica)
-2
-3
-4
-4
-3
-2
-1
Velocity (mm/s)
Figure 7
Mossbauer
spectra of mineral species representing the regions shown in Figure 6 (mineral
group names are given in parentheses; staurolite does not belong to any group). Tetrahedral
Fe3+ dominates the spectrum of an unusual nonmarine glauconite from Hurricane Mountain,
New Hampshire (sample courtesy of Carl Francis). The jarosite structure contains
Fe3+ (OH)4 O2 octahedral rings; this sample is a synthetic composition, #14B from Brophy &
Sheridan (1965). Staurolite is one of the few common mineral species to contain tetrahedral
Fe2+ ; the sample shown here is 356-1 from Dyar et al. (1991). Olivine is a typical silicate
containing octahedral Fe2+ ; this forsterite is from San Carlos (unpublished data). Almandine
from Fort Wrangell, Alaska, here represents the Mossbauer

spectrum of Fe2+ in pseudocubic,
eightfold coordination in the garnet structure (Dyar 1984). Spectra are normalized to 4%
absorption and stacked with a 3% offset for clarity. All data collected in Dyars laboratory.
96
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Table 1
17 April 2006
Typical 295 K Mossbauer

parameters of rock-forming minerals
Dana class

23:19
Species or
group name
IS
QS
Site
or Bhf
Iron
0.00
0.00
Suldes
Chalcocite
0.33
0.56
Music et al. (1981)
Bornite
0.36
0.21
Gallup & Reiff (1991)
Sphalerite
0.60
0.63
Troilite
0.77
0.08
Stannite
0.52
2.91
Baldini et al. (1989)
Pyrite
0.29
0.60
Various workers
Marcasite
0.28
0.49
Various workers
Arsenopyrite
0.30
1.15
Various workers
Tochilinite
1.16
2.77
This work; preliminary

results
Franckeite
0.23
0.55
Huang (1987)
0.95
1.77
0.34
0.43
0.59
2.54
0.53
2.22
0.35
0.29
0.49
1.30
0.95
0.44
0.90
0.79
Hematite
0.37
0.20
Ferrihydrite
0.35
0.83
0.35
0.90
0.36
0.52
1.04
0.70
0.20
0.27
Sulfosalts
Tetrahedrite
Tennantite
Simple oxide
Wustite
Ilmenite
Hydroxide
Oxide
33.1
References(s)
Native element
Various workers
Various workers
31.3
Various workers
Charnock et al. (1989)

Makovicky et al. (2003)
Murad & Johnston (1987)

51.8
Various workers
Virgo et al. (1988)
Maghemite
0.32
0.02
49.9
Goethite
0.37
0.26
38.2
Lepidocrocite
0.37
0.53
Akaganeite
0.38
0.55
0.37
0.95
0.82
1.62
1.18
1.56
0.26
0.02
49.0
0.67
0.00
46.0
1.11
1.75
0.90
0.96
0.86
1.63
0.31
0.79
Hercynite
Magnetite
Spinel

Various workers
Various workers
(Continued)
97
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23:19
Table 1
(Continued )
Dana class
Species or
group name
QS
0.32
0.44
0.22
0.91
0.96
0.50
0.90
1.15
Ulvospinel
1.07
1.85
Various workers
Multiple oxides
Columbite
1.15
1.55
Garg et al. (1991)
Anhydrous
carbonates
Siderite
1.22
1.80
Various workers
Ankerite
1.23
1.50
Various workers
Hydrous
sulfates
Szomolnokite
1.28
2.75
0.65
0.35

results
1.29
3.30
1.27
2.76
0.39
0.35
0.13
0.49
1.25
2.86
1.27
3.50
0.46
0.67
0.18
0.46
1.28
2.73
1.30
3.35
1.32
1.70
0.45
0.36
0.14
0.51
0.11
0.63
0.46
0.38
0.27
0.52
1.22
1.58
1.34
1.79
0.46
0.41
0.17
0.65
Chromite

Site
or Bhf
IS
Romerite
Melanterite
Halotrichite
Coquimbite
Voltaite
References(s)
Kuno et al. (2000)

results

results

results

results
results
Anhydrous
sulfate
Jarosite
0.37
1.20
Various workers
Hydrated
phosphate
Phosphoferrite
1.19
2.45
1.19
1.57
Mattievich & Danon

(1974)
1.21
2.98
1.18
2.45
0.38
1.06
0.40
0.61
1.12
3.32
0.40
0.47
Vivianite
Anhydrous
phosphate
Lazulite
Amthauer & Rossman

(1984)
Amthauer & Rossman

(1984)
(Continued)
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Table 1
17 April 2006
(Continued )
Dana class

23:19
Species or
group name
IS
QS
0.38
1.37
0.41
0.90
Site
or Bhf
References(s)
Hydrated
phosphate
Strunzite
0.41
0.36
Anhydrous
tungstate
Ferberite
1.11
1.49
Caruba et al. (1982)
Orthosilicates
Willemite
1.02
2.92
Holtstam (2002)
1.09
2.57
0.35
0.34
Fayalite
1.14
3.10
Various workers
Forsterite
1.14
2.93
Various workers
Zircon
0.27
1.03
0.21
Disilicates
Carreto et al. (2001)

51.83
Almandine
1.29
3.53
Various workers
Andradite
0.40
0.55
Various workers
Staurolite
0.98
2.44
Fe1
Dyar et al. (1991)
0.98
2.08
Fe3
0.97
1.55
Fe2
0.89
0.93
Fe
1.05
0.83
0.11
0.79
1.12
2.42
0.29
0.96
0.42
1.70
0.34
1.14
1.20
2.56
1.09
3.33
1.07
1.62
0.36
1.78
0.33
0.85
1.30
2.12
0.57
0.39
0.17
0.51
0.43
0.82
0.77
1.21
ED
1.09
2.47
1.09
2.19
1.07
1.60
1.16
2.70
Sample courtesy of L.
0.59
0.86
Groat; preliminary results
1.19
2.30
Khomenko et al. (2001)
Chloritoid
Pumpellyite
Epidote
Ferroaxinite
Ring silicates
Vogel & Evans (1980)
Schorl
(tourmaline)
Beryl
Cordierite
Koch-Muller et al. (2000)

Artioli et al. (2003)
Kartashov et al. (2002)
Astakhov et al. (1975)

Dyar et al. (1998)
(Continued)
99
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23:19
Table 1
(Continued )
Dana class
Pyroxenes
Species or
group name
QS
1.18
2.49
M1
1.13
1.91
M2
1.18
2.21
M1
0.34
0.68
M1
1.16
1.87
M1
1.15
2.14
M2
DeGrave & Eeckhout

(2003)
0.30
0.77
Burns & Dyar (1991)
0.40
0.84
1.20
2.41
1.11
2.85
M1
1.12
1.80
M2
1.11
2.40
M3
1.11
2.05
1.06
2.41
0.39
0.87
1.13
1.90
M2
1.13
2.86
M1+M3
0.35
0.53
1.20
2.42
M1+M5
1.12
2.02
M4+M7
1.03
1.30
M8
0.36
1.09
M2
0.31
0.92
M3+M6
+ M9
Clintonite
0.47
0.51
Wang & Zhengmin (1992)
Chlorite
0.25
0.50
Smyth et al. (1997)
1.09
2.59
1.11
2.33
1.14
2.66
0.12
0.39
0.35
0.40
0.35
0.65
1.12
2.61
0.36
0.61
1.13
2.57
1.12
2.15
0.40
0.87
0.20
0.75
1.13
2.57
1.12
2.15
Ferrosilite
Hedenbergite
Diopside

Pyroxenoid
Amphiboles
Babingtonite
Tremoliteactinolite
Kaersutite
Winchite
Chain silicate
Sheet silicate
Site or
Bhf
IS
Surinamite
Illite
Phlogopite
Talc
References(s)
Dowty & Lindsley (1973)
Eeckhout & DeGrave
(2003)
Burns & Greaves (1971)
Dyar et al. (1993)
Gunter et al. (2003)

Barbier et al. (2002)
Murad & Wagner (1994)

Various authors
Coey et al. (1991)

(Continued)
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Table 1
17 April 2006
(Continued )
Dana class
Species or
group name
Kaolinite
Glauconite
Lizardite

23:19
Chrysotile
Framework
silicates
Feldspar
Site or
Bhf
IS
QS
0.41
0.46
1.11
2.53
1.11
2.71
0.33
0.45
0.34
0.99
1.14
2.70
0.40
0.70
0.24
0.39
1.13
2.75
0.31
0.86
0.18
0.33
1.14
2.12
0.92
2.09
1.09
1.45
0.19
1.22
0.55
1.33
0.24
1.19
References(s)
Murad & Wagner (1991)
Ali et al. (2001)
OHanley & Dyar (1993)
OHanley & Dyar (1998)
Dyar et al. (2002b)
All values of IS are referenced to the midpoint of an -Fe spectrum. IS and QS are given in mm/s and Bhf
in tesla. For site occupancies, T = tetrahedral site, M = octahedral site, and 8 = 8-coordination; in some
cases, mineral-specic site names are given. If no assignment is given in the citation, none is given here.
Shaded cells represent data for which information was not given.
IS is extremely sensitive to the oxidation state of the sample. IS values predictably

decrease with increasing s-electron density around the nucleus, so they depend not
only on oxidation state but also on the type and bond lengths of ligands coordinated
to the Fe atoms. In minerals and silicate glasses, Mossbauer

parameters are conned
to relatively small ranges. Parameters for Fe3+ cover a relatively small range in IS. In
silicates and oxides, high metal-oxygen distances in coordination polyhedra result in
higher values of isomer shift. The upper limit for Fe3+ in tetrahedral coordination
is approximately 0.25 mm/s, whereas the lower limit for octahedral Fe3+ is approximately 0.29 mm/s (Burns & Solberg 1988). For Fe2+ , values of IS > 1.20 mm/s are
generally attributed to eightfold or dodecahedral coordination, values of 1.20 > IS >
1.05 mm/s are generally octahedral, and values of 1.05 > IS > 0.90 mm/s are assigned
to tetrahedral occupancy.
Quadrupole splitting is sensitive to oxidation state and site geometry. As an example, consider Fe2+ in perfectly octahedral (sixfold) coordination. The electronic
4 2
conguration of Fe2+ , 3d6 , is in general high spin for minerals, i.e., t2g
e g . The sixth
electron populates the three degenerate (all the same energy) t2g levels equally, so
spherical symmetry is maintained and, neglecting lattice terms, there is no quadrupole
splitting. A distortion of the octahedral environment, as occurs through Jahn-Teller
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23:19
distortion, lifts the degeneracy of the t2g levels, leading to unequal occupancy of the
d orbitals and a large contribution to QS from the electronic eld. In high-spin Fe3+ ,
3 2
which has electronic conguration t2g
e g , the d orbitals remain equally populated even
when the octahedral environment is distorted, and the electronic eld remains spherical. Of course, in both cases, asymmetry in the lattice eld causes [6] Fe2+ and [6] Fe3+
to split the I = 3/2 level, but in general, QS for Fe2+
QS for Fe3+ . Furthermore
(as a general rule), the larger the QS, the more distorted the coordination polyhedron
surrounding the Fe atom.
For phases that show hyperne splitting, the magnitude of the magnetic eld
can be useful in distinguishing among phases with similar IS and QS. This is useful in identication of such phases as iron oxides at room temperature and in lowtemperature studies, comparing the hyperne split low-temperature spectra to their
simple quadrupole-split room-temperature counterparts.
Mossbauer
parameters of minerals (and everything else!) can be found by search
ing the comprehensive online, subscription database maintained by the Mossbauer
Effect Data Center (MEDC, at http://www.unca.edu/medc/). This resource, which
includes all published Mossbauer

papers back to and including Professor Rudolf L.
Mossbauers
original paper in 1958, contains over 80,000 records, is the result of
a 30-year effort, and is updated monthly. Its strength, which lies in its incredible
breadth of coverage, unfortunately somewhat limits its usefulness: Parameters listed
there come from publications of all types and are simply reported from the literature
without judgment of their reasonableness. Although the MEDC provides an excel
lent starting point for understanding Mossbauer
parameters of any given material,
it is always necessary to consult the original papers to evaluate the conditions and
constraints with which data were generated.
The MEDC compiles parameters only. Our research group maintains an on
line library of Mossbauer
spectra (and ASCII data) of many rock-forming minerals at
www.mtholyoke.edu/courses/mdyar/database. Although our site is largely limited
to data collected in our own laboratory, it presents typical spectra from many mineral
groups, and is intended as a teaching resource for the community.

ANRV273-EA34-04
INSTRUMENTATION
The basic elements of a Mossbauer

spectrometer are a source, a sample, a detector,
and a drive to move the source or absorber. Most commonly, this is done by moving
the source toward and away from the sample while varying velocity linearly with time.
For example, for 57 Fe, moving the source at a velocity of 1 mm/s toward the sample,
by Equation 2, increases the energy of the emitted photons by (14.413 keV)(v/c) =
4.808 108 eV, or approximately ten natural linewidths. Thus, mm/s is the
conventional energy unit in Mossbauer

spectroscopy. It is also possible to leave the
source stationary and oscillate the sample, as is done with synchrotron Mossbauer
(cf. Handke et al. 2005). The location of the detector relative to the source and the
sample denes the geometry of the experiment (Figure 8); most commonly, either
transmission or backscatter modes are used.
102
Dyar et al.
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17 April 2006
23:19
Collimator
Detector
Mssbauer drive

57
Co
source
Sample
Figure 8
A comparison of the
different geometries for
transmission (a) and
backscatter (b) Mossbauer

spectroscopy (adapted from
Shelfer 1992) and ILEEMS
(c). Adapted from DeGrave
et al. 2005.
Sample
Collimator
Mssbauer drive
57
Co
source
Detector
Mssbauer
drive
Detector
(Channeltron)
e-
57
Co source
Sample
Collimator
to pump
Transmission Mode Experiments
The instrumentation for Mossbauer

experiments is well described by Bancroft (1973)
and updated by Murad & Cashion (2004), so only a brief update is needed here.
The vast majority of Mossbauer

experiments in the geosciences are conducted in
transmission mode, where the gamma path leads directly from source to detector
and just one event is of importance (resonant gamma absorption), the velocity is
well dened, and, for a thin absorber (sample), the resulting spectrum is a simple
superposition of spectra of the individual mineral components.
Recent major advances in spectrometer design have made it possible to study
samples with either low total Fe contents or low sample mass; such a design is now
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17 April 2006
23:19
commercially available from WEB Research Co. of Minneapolis, MN. For the low
sample masses, this involves use of a strong 57 Co source (50100 mg) as well as
constraining the combination of source size, sample shielding, and alignment while
minimizing the amplitude of the emitter (source) motion to make it possible to use
samples with 0.5 cm mount diameter. This represents a sample area (which is lled
with a mixture of sample plus a dispersing medium that acts as a ller, usually sucrose)
that is only 5% of the sample area used in older instruments. This improvement in
technology means the difference between handpicking 510 mg of pure mineral (a job
that takes less than an hour even in extremely ne-grained samples) versus 200300
mg (a weeks job for the best pickers!).
The new instruments make it possible to position the source within only a few
millimeters of the sample, even at 4.2K, while retaining linewidths of 0.22 mm/s for
the central lines of an Fe foil. In our laboratory, this change in geometry initially
doubled our count rates with a standard Kr gas counter and a single SCA counting system; the subsequent substitution of a scintillation detector improved count
rates by an additional 60%. With the current apparatus, >1,000,000 baseline counts
per hour can be acquired on a sample with ideal thickness when a 100 mCi source
is used. Thus, a spectrum that once took 12 days to acquire can now be generated in one hour! Even with very short runs, data of outstanding quality can be
acquired.
Data quality can be further enhanced by correcting for (nongamma) Compton
scattering, which contributes to the background within the 14.4-keV single-channel
analyzer window in every measurement. The % Transmission scale on Mossbauer

plots can then be corrected to refer only to transmitted gamma photons. The fraction
of the baseline owing to the Compton scattering of 136 keV and 122 keV gammas
off counter gas electrons can be determined by measuring the count rate with and
without a 14.4-keV stop lter in the gamma beam (we use 200 m of Al foil). If
b is the Compton fraction and A is the uncorrected absorption, then the Comptoncorrected absorption is A/(1 b). This correction provides an absorption scale that
is fairly independent of the type of gamma detector used, but it must be calculated
for each individual sample. The resultant improvement is worth it.

ANRV273-EA34-04
Mossbauer
Milliprobe
A highly successful adaptation of the powdered sample Mossbauer

apparatus for transmission experiments has been the milliprobe developed by Catherine McCammon
at Bayreuth (McCammon et al. 1991, 2000; McCammon 1994; Sobolev et al. 1999).
This modication, which uses a lead plate to restrict gamma rays to a small diameter
(100 m), can be used to study single grains in thin sections or single crystals. Its
application is limited by the need to know the orientation of the electric eld gradient (EFG) tensor in various mineral groups to overcome the texture effects imposed
by study of anisotropic crystals; such work is indeed ongoing (e.g., Tennant et al.
2000). Many studies using the milliprobe technique have been made, most recently
including Partzsch et al. (2004), McCammon et al. (2004a,b), and Bromiley et al.
(2004).
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Backscatter Geometries
Backscatter Mossbauer
spectra (illustrated schematically in Figure 8b) are acquired
while detecting radiation emitted by the sample/absorber as function of source velocity, either the 14.4-keV gamma or 6.4-keV X-ray photons. They contrast with
transmission measurements, which simply report whether resonant absorption occurs, in that they incorporate multiple internal events, both nuclear and extranuclear
(atomic). Source gammas strike the sample at various angles and initiate a complex series of events involving gamma photons, X-rays, and electrons, leading to a
complex radiation path, which may be multiply branched. The detected radiation
exits the sample at various angles before striking the detection surface and contributing to the backscatter spectrum, so that the interrogated portion of the rock or
soil is not simply related to photoelectric attenuation coefcients for 14.4 keV and
6.4 keV.
Although the principles of backscatter theory are well established (e.g., Balko &
Hoy 1974, Bara & Bogacz 1977, Bara 1980); and particular geometries have been
modeled (e.g., Jaggi 1982, Fultz & Morris 1986, Mei 1987, Lefman 1991), until recently literature on its application has been sparse owing to its infrequent utilization
in the laboratory. The application of the theory must be developed anew for each
particular situation because it is strongly dependent on the geometry of both sample and backscatter instrument, in particular in the case where source, sample, and
detector are all extended objects. To properly apply backscatter theory, the theory
must incorporate all the various events that occur, and an optimal method for summing contributions to the observed backscatter spectrum must be developed, based
on an integration over angles or a simulation of paths followed by individual incident gamma photons leading to the detected 14.4- or 6.4-keV photons, such as via
so-called Monte Carlo methods.
The dramatically different geometry of the backscatter instrument makes proper
interpretation signicantly more complex than the usual transmission-mode experiments. Geometry-related considerations that must be taken into account for analysis
of backscatter data include the following:

Spread of 57 Co nuclei in the Mossbauer

source and appearance of resonantly
absorbing 57 Fe nuclei as the source ages (emission prole)
Angular spread of emitted gamma photons (velocity prole)
Distance of source from interrogated surface
Area of interrogated surface exposed to source radiation
Distribution of detector surfaces (silicon PIN detectors are used on the Mars
rover instruments, discussed below)
Differences in 14.4- and 6.4-keV spectra, i.e., those acquired while detecting
gamma or Fe K X-ray photons
Despite the complexity in modeling backscatter measurements, they are the only
practical application of this technique for planetary exploration. The remarkable
Mossbauer
instruments on the Mars Exploration Rovers (MERs), the MIMOS II
spectrometers, are described in Klingelhofer

et al. (2003). Many examples of spectra
obtained with MIMOS II and similar miniature backscatter instruments are available
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MER: Mars Exploration

Rover

EDR: experimental data

record
23:19
in the literature (e.g., Klingelhofer

1998; Shelfer & Morris 1999; Klingelhofer
et al.
2003, 2004; Wdowiak et al. 2003; Morris et al. 2004).
Analyses published by the MER team (Klingelhofer

et al. 2004, Morris et al.
2004) have provided dramatic new insights into the nature of Mars surface material,
for example, suggesting the presence of minerals produced in the presence of water.
However, to accommodate relatively poor counting statistics (compared to laboratory expectations), compromises in the data tting were adopted by the MER team.
These include summing of spectra acquired under different conditions, e.g., at variable temperatures, with consequent loss of information; modeling spectra as sums
of Lorentzians, with limited consideration of geometric, i.e., saturation, effects that
lead to line distortions; and ignoring the half of the data collected in the 6.4-keV
channel.
Beginning in August 2004, raw data acquired by the Mossbauer

spectrometers
on the Mars Exploration Rovers (MERs) have been released to the science community as experimental data records (EDRs) for each Martian day (sol) on which
measurements were made. To provide convenient direct access to the EDRs, to enable independent assessment and analysis, and to allow conrmation of MER-team
scientic conclusions, a new Windows-based computer program, MERView, has been
developed (Agresti et al. 2005a,b). Correction for nonlinearity is done using the EDRprovided drive error signal, a phase shift, and the requirement that the two halves of
a reference spectrum must overlap exactly when plotted on a correct velocity scale
dened relative to the maximum drive velocity (Vmax ). Converting the scale from
%Vmax to mm/s is less straightforward.
Each of the MERs has a unique reference target used for calibration purposes,
so that a reference spectrum can be acquired at the same time as each spectrum of
a surface sample. The reference samples on the MERs consist of a mixture of -Fe,
hematite, and magnetite (Klingelhofer

& Squyres, personal communication, 2005),
although the relative proportions of these components are unknown. Laboratoryacquired spectra of the reference targets at temperatures experienced on Mars would
be desirable, but these data have not been released by the MER team. The reference spectra are extremely complicated, and the targets on the two rovers are quite
different. In both cases, the overlap of the hematite and magnetite subspectra is too
great to allow them to be used directly for calibration. In the reference spectra there
are four peaks arising from -Fe that are relatively free of overlap with the hematite
and magnetite subspectra (the other two peaks of the -Fe sextet cannot be clearly
resolved). We are using these four peak locations (at roughly 5.32, 3.08, 0.84, and
3.08 mm/s) to provide the mm/s calibration. MER spectra that have been corrected
for nonlinearity and calibrated using this method are available on the Mount Holyoke
Web site at http://www.mtholyoke.edu/go/mars.
ILEEMS
ILEEMS is an exciting new technique that utilizes the low-energy electrons emitted by the nuclei in the sample [the lowest-energy (E < 15 eV) and shake-off
electrons in Figure 3]. The geometry of the apparatus is shown in Figure 8c.
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Because the energy of these electrons is so low, their origin within the sample lies at
a depth of only a few nanometers. Therefore, this technique is ideally suited to the
study of surface processes and alteration in iron-bearing materials. This technique
has just recently been brought to bear on materials of geologic interest by DeGrave
et al. (2005), who are nding that ne layers of hematite are present on the surfaces of several other iron oxides in amounts that cannot be detected by any other
technique.
INTERPRETATION OF MOSSBAUER
DATA
Mossbauer
Lineshapes
As discussed earlier, the intrinsic emission spectrum is a Lorentzian centered at E0
with linewidth, 0 (Figure 1). That is, the probability distribution of the energy, E,
of emitted recoilless gamma photons is given by

1
,
(6)
L S (E, v; E0 , 0 ) =
2 (E E0 E0 v/c )2 + (0 /2)2
Doppler shift: in
Mossbauer
spectroscopy,
the relative shift in energy
of a photon, typically the
gamma photon emitted in a
Mossbauer
transition,
achieved by moving the
radiation source toward or
away from a resonant
absorber with a certain
Doppler velocity
where the source is assumed to be moving with relative velocity, v, so that, by Equation
1, the center of the spectrum is Doppler shifted to E0 + E0 v/c. A single-line, i.e.,
unsplit, absorption spectrum has in principle also a Lorentzian lineshape, but with
xed center at E0 + IS, where E0
IS (cf. Figure 4, red, and Figure 5, blue). It is
thus of the form L A(E; E0 + IS, A), where the velocity variable, v, has been omitted
and the absorption linewidth is A = 0 , as might be the case if values for IS were
distributed while preserving the Lorentzian lineshape.
As seen in Figure 4 (blue), the transmission spectrum dips from the baseline
because resonant absorption of incident gamma photons changes as v is varied. For
thin absorbers where the Compton-corrected absorption (see earlier) is no more
than 5%10% depending on the precision required, Margulies & Ehrman (1961),
showed that the resonant absorption is given by the overlap integral,
+
(7)
L S (E, v; E0 , 0 ) L A (E; E0 + IS, A)dE = L A (v; IS, 0 + A) ,
which is a Lorentzian function of v centered at IS with linewidth 0 + A, where the

latter two quantities are now expressed in velocity units.
If the absorption spectrum is more complex (Figure 5, red and green), in the thin
absorber limit it is then simply a sum of Lorentzians, and L A(. . .) in Equation 7 is
replaced by a weighted sum over functions, L A(E; E0 + Ei , i ), where Ei , and i
refer to the individual absorption transitions. The transmission spectrum can then
be modeled as a baseline minus a sum, or superposition, of Lorentzian lines with
different positions, linewidths, and intensities (or areas). Note that these line properties are generally not independent of each other, as shown in Figure 5, where line
positions are given by the Mossbauer

parameters, IS, QS, and Bhf for each distinct Fe
nuclear site, linewidths are equal, and intensities are in the ratio of 1:1 or 3:2:1:1:2:3.
Peak properties are dened by the Mossbauer

parameters and other correlations, and
not the other way around!
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When the thin absorber limit is exceeded, special care must be exercised in modeling the transmission, as it is no longer a superposition of Lorentzians. Ideally, a transmission integral is computed that accounts for saturation of the resonance absorption that occurs for thick absorbers, which tends to atten, or round, the deeper
portions of the spectrum, increasing effective linewidths and distorting spectral
areas. Why does such saturation occur? If (v) is the resonant absorption probability
per unit thickness and tA the thickness, then transmission I(v) = I0 exp[(v) tA]. For
thin absorbers, I(v) I0 I0 (v) tA , and the absorption is proportional to (v) at all
velocities, so no distortion occurs. For larger tA, this approximation works for smaller
(v), but not larger (v), which then lie on the rounded portion of the exponential,
leading to less transmission than if the linear approximation were still valid at that
velocity.
The transmission integral was derived for a single-line absorber by Margulies &
Ehrman (1961) and for hyperne splitting of the emission and absorption lines by
Margulies et al. (1963). Because of its complexity and the time required to compute
the integral repeatedly at each step in an iterative least-squares tting routine,
workarounds are typically employed, such as various corrections for saturation or
use of lineshapes that are more rounded than the Lorentzian. With such approxima
tions, precision in the Mossbauer
parameters is somewhat compromised, and relative
areas more so.
If several species of iron (i.e., different coordination states, coordination environments, etc.) contribute to a spectrum, then the total area of all the Lorentzian lines
for each species is directly proportional to the number of atoms of that species. In
the simplest analysis, relative site populations are determined by nding areas ratios.
More precisely, the areas are proportional to the true populations by the following
formulation (Preston et al. 1962, Bancroft 1967, 1969):

ANRV273-EA34-04
A1
n1
=C
A2
n2
where C =
1 f1 G(X1 )
,
2 f2 G(X2 )
(8)
and G(X ) is a saturation factor that depends, in part, on the thickness.

To put this in mineralogical terms, consider a simple example where two minerals
(olivine and pyroxene) each have only Fe2+ in octahedral coordination. The doublets
2+
2+
2+
corresponding to Fe2+
ol and Fepx have areas equal to Aol and Apx ; n is the true amount
of each species and C is the correction factor. Using the formulation given above, we
nd that
A2+
n2+
ol fol G(Xol )
ol
.
(9)
= C ol
where C =
2+
Apx
n2+

px f px G(Xpx )
px
Thus, to determine true site and valence state information from a Mossbauer
spectrum
from the Martian surface (or from a terrestrial laboratory) it is necessary to consider
three factors:
1. The equal linewidth () assumption is only reasonable in end members, but
most tting routines can allow linewidths to vary.
2. The saturation corrections for G(X) can be avoided if thin absorbers are used.
However, for the backscatter mode spectra acquired on the Martian surface,
understanding the extent of variation of G(X) will be a problem.
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3. As noted above, recoil-free fractions depend greatly on site geometries and valence states, and thus different values of f are likely in cases where two sites have
radically different geometries. Whipple (1968) has suggested that variations in
C can inuence the results of Mossbauer

Fe3+ /Fe2+ ratios in silicates by up
to 30%; much of this error is due to variations in f . DeGrave & van Alboom
(1991), who worked on oxides and oxyhydroxides, found that failure to consider
effects of differential f could lead to errors averaging 15% for Fe3+ /Fe2+ . Thus,
quantitative determinations of f are critical to obtaining useful site occupancies
and valences states.
Recoil-Free Fraction
Given the preceding discussion, it should come as no surprise that one of the active
areas of Mossbauer
research on minerals is the determination of recoil-free fractions
in a systematic way. There are at least four ways to evaluate differential recoil-free
fraction. The rst, somewhat brute force method is to measure the Fe3+ /Fe2+ in a
number of samples of a given mineral species using an independent technique (e.g.,
wet chemistry), and then to calculate a value for C based on equations given in Bancroft
(1969). This method was used by Bancroft & Brown (1975), who inferred an average
value of C = 0.98 0.04 for biotite, and by Whipple (1968), who made some very
careful comparisons between Mossbauer

and wet chemical data. These correction
factors apply only to the specic compositions used in these studies, and do not apply
to measurements at temperatures other than 300 K.
A second way to determine C is to calculate f using Mossbauer

single-crystal
measurements, as described in Tennant et al. (1992) and Tennant (1992). In this
technique, the relationship between the Mossbauer

fraction and the mean squared
displacement (MSD) tensor (cf. Equation 5) is used to derive the Mossbauer

fraction
from a set of single-crystal Mossbauer

spectra. Although this method has been proven
workable, in the words of Tennant (1992), The disadvantages are the difculties
in obtaining a meaningful MSD tensor, and the (consequent) tedious nature of the
experiment.
The third and fourth approaches both model the lattice-vibrational spectrum of
57
Fe using the Debye approximation (e.g., Frauenfelder 1962, Goldanskii & Herber
1968). In the Debye approximation, the absorber is assumed to be isotropic and
elastic. Its vibrations have a nite range of frequencies characterized by the Debye
temperature, D , which is proportional to the maximum vibrational frequency of the
lattice. All the directions of emission of phonons have equal probabilities. This model
oversimplies complex lattice systems, especially in the region of high frequencies
(Goldanskii & Herber 1968), but as long as it is used in the comparison of structurally
similar systems, it appears to be an adequate approximation (Eeckhout & DeGrave
2003). The third method determines f by measuring the temperature dependence of
peak areas and relating that back to f by means of the thickness parameter (Laeur
& Goodman 1971).
A fourth approach to quantifying f is to use the temperature dependence of the
center shift (IS). Mossbauer

spectra of the mineral of interest are acquired over a range
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Recoil-free fraction (f ):
fraction of times a photon is
emitted or absorbed without
energy transfer to (or from)
the host lattice in a
Mossbauer
transition, i.e., a
transition that can exhibit
the Mossbauer
effect, such
as the 14.4-keV ground to
rst-excited state transition
in 57 Fe
23:19
of temperatures, usually from 2050 K up to 600800 K, at 1050 K increments. The

temperature dependence of the center shift is t to the Debye integral approximation
to determine a value for D and I using

9 k B T T 2 D /T x 3 d x
,
(10)
IS(T ) = 1
2 Mc D
ex 1
0
where I is the intrinsic isomer shift, M is the mass of the Mossbauer

nucleus, and D
is referred to as the characteristic Mossbauer

temperature, M (DeGrave et al. 1985).
A large value for M suggests a stiff lattice.
Next, the tted value for D is used in the Debye integral approximation for the
recoil-free fraction to calculate f(T) for each site using the relation:

2 D /T
3 ER
T
xd x
f (T ) = exp
+ 1+4
.
(11)
2 kB D
D
ex 1
0
Note from this expression that when D is large, f will be large. Thus, higher values
of f are indicative of more tightly bound atoms.
Further information on this method can be found in Herberle (1971), Grant
(1995), and DeGrave et al. (1985). Such determinations of the recoil-free fractions for
Fe3+ and Fe2+ in assorted minerals by DeGrave & van Alboom (1991) and Eeckhout &
DeGrave (2003) have shown that f values are strongly mineral, site, and composition
dependent. Rancourt (1994) found that recoil-free fractions were equal for all sites in
a synthetic annite within experimental error. A related thesis by Royer (1991) made a
detailed study of site-specic recoil-free fractions in Fe-bearing trioctahedral micas
and apparently found larger f values for Fe3+ in micas than for Fe2+ (as reported in
Rancourt 1994). The overview paper by Eeckhout & DeGrave (2003) summarizes
most of the known f values for minerals. Characterization of f values for common
rock-forming minerals is ongoing in our research group (Rothstein et al. 2005, Sklute
et al. 2005). Values for f typically range from 0.65 to 1.
It is worth noting that values of f determined by this method rely on a somewhat unrealistic approximation of the Debye model, and the calculated M has little
physical meaning. However, f values determined in this way do have value as phenomenological parameters, and they do allow comparison of different lattice sites
within a given compound or in the comparison of structurally related compounds
(DeGrave & van Alboom 1991). Some ground-truth comparisons of f values have
been made using this method. DeGrave & van Alboom (1991) acquired Mossbauer
spectra of binary mixtures made with known relative contents of different minerals
(hematite, goethite, lepidocrocite, ilmenite, and ferrochromite) and compared the
resultant peak areas with f values determined using the method just described. The
agreement between calculation and experiment was within 0.035 or closer. However,
for some purposes, additional measurements of mixed minerals may be desirable.
Fitting Mossbauer
Data
Techniques for processing Mossbauer

data are complex and variable. There are
at least four popular Mossbauer

spectral analysis programs, used to interpret the
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spectra of geologic (and other) materials. Mossbauer

spectra of minerals frequently
exhibit highly overlapping peaks, and under these conditions the particular tting
techniques and model assumptions used can make a difference in how the spectra
are interpreted. Typically, members of a research group will use only one of these
spectral analysis programs, and differences in interpretation that might arise from
the use of different programs are therefore virtually unknown. In addition, there are
many physical models that have been applied to interpret Mossbauer

spectra, and
there have been very few published comparisons of any of these models (e.g., Rancourt 1994, Lagarec & Rancourt 1997). In Rancourt (1994), tting with Lorentzian
line doublets was compared to tting with quadrupole splitting distributions (using
the Recoil program). In the quadrupole splitting distribution model (as in the hyperne eld distribution model for magnetically split spectra), any broadening of the
absorption lines beyond their intrinsic linewidth is assumed to be due to a Gaussian
distribution of static hyperne parameters, producing Voigt-shaped lines (Rancourt
& Ping 1991).
Software for analysis of Mossbauer

spectra uses a variety of different physical
models to generate model spectra with which to compare the measured spectra, and
different tting algorithms to analyze the data. It is important to assume a theoretically
reasonable model when tting Mossbauer

spectra because it is possible, based on the
data alone, to t spectra to an unphysical model and still get supercially reasonable
chi-squared values.
There are at least four most commonly used, easily available computer
programs. These include WMOSS, from WEB Research Co. in Minnesota
(http://www.webres.com, originally commercial, but recently released to the public domain); Recoil, from the University of Ottawa, in Canada (http://www.
physics.uottawa.ca/recoil/, a commercial product); MossWinn, from Lorand
os
University, in Hungary (http://www.mosswinn.com, a commercial prodEotv
uct); and an in-house suite of programs from the University of Ghent, in Belgium
(referred to here as the Ghent programs). WMOSS is capable of assuming seven
different physical models in its tting, including quadrupole splitting distributions
with Voigt-based tting and hyperne eld distributions with Voigt-based tting. It
can use any of ve different tting algorithms. Recoil may assume all these models,
as well as several others, and is capable of calculating full Hamiltonians. MossWinn
(Klencsar et al. 1998) uses pseudo-Voigt functions and calculates an exact solution
of the nuclear Hamiltonian, although it, too, calculates the quadrupole splitting distribution and hyperne eld distribution. The Ghent programs [based on Wivel
& Mrup (1981)] can use discrete quadrupole splittings or distributions, discrete
hyperne elds, or distributions, with Lorentzian lineshapes and the capability of
correlating isomer shifts with quadrupole splitting or hyperne eld distributions. In
addition, they also have the capability of calculating full Hamiltonians.
Preliminary results of our ongoing study to compare these four programs highlight
the necessity for intelligent and thoughtful tting of Mossbauer

spectra (Schaefer &
Dyar 2005). It is possible to produce ts of a single, relatively simple spectrum that
have similar chi-squared values but signicantly different Mossbauer

parameters or
even numbers of peaks. Initial estimates of peak parameters and use of constraints can
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have dramatic effects on ts. Results can be highly variable, not only between programs but also while tting with one program alone. Clearly more work must be done
to determine the causes of this variability and the best methods of interpreting these
results. This is important not just to the interpretation of present and future spectra,
but to the understanding of spectra and Mossbauer

parameters in the literature.
Other Constraints

One nal and fundamental constraint on geological applications of Mossbauer

re
sults must be mentioned because it is frequently misunderstood. 57 Fe Mossbauer
spectroscopy can determine only the relative amounts of iron in various types of
sites and valence states. It cannot determine the total number of Fe atoms that are
present in a material (i.e., relative to the other atoms present) because the presence of
other elements has no effect on the Mossbauer

spectrum except as they alter the Fe
environment and reduce the overall intensity of the spectrum, but not its dependence
on velocity. It should be emphasized, therefore, that Mossbauer

spectroscopy is a tool
to investigate the nature and relative contents of Fe-bearing minerals in a sample. It
provides no information on minerals that do not contain Fe in their structures.
NEW DIRECTIONS
In recent years, the elds of mineralogy, geochemistry, and petrology have become
more dependent on microanalytical techniques. The recent improvements in instru
mentation for and modeling of Mossbauer
spectra have opened up possibilities for
analysis of a much broader range of materials than ever before because low-Fe materials and small sample quantities can now be studied successfully. These advances
are expected to turn the interest of the scientic community once again to the study
of Fe3+ and Fe2+ partitioning in a wide variety of geological materials.
Three examples of applications of Mossbauer

spectroscopy serve to illustrate these
advances. The rst involves the study of Fe in feldspar, which is the most common
mineral group in Earths crust. Because feldspar is so low in Fe, it has not been studied
with Mossbauer
spectroscopy since the 1970s-era papers on Apollo lunar samples,
but new spectrometers can easily analyze feldspar, and even discriminate between Fe
in feldspar and Fe in oxide inclusions. We are currently studying the valence state of
iron in plagioclase within the Pyroxenite Marker (PM) magma inux in the Bushveld
Complex (Lundgaard 2003). The FeOTotal contents of plagioclase increases systematically within the 400-m-thick mixing zone below the PM at Roossenekal from
0.39 wt% at 383 m to 0.63 wt% at 6 m, followed by an abrupt decrease to 0.48
wt% 25 m above the PM. This overall increase in FeOTotal of the plagioclases across
the PM is opposite to the coexisting orthopyroxenes that show iron depletion. One
explanation for this apparent discrepancy is that the new magma added had higher
FeOTotal and Mg-number than the resident magma. Another interpretation of the
increase in FeOTotal of plagioclase is that the new magma had higher oxygen fugacity,
which would be reected in plagioclase Fe3+ /
Fe contents. To evaluate these
hypotheses, we have acquired Mossbauer

spectra on plagioclase separates (Figure 9);
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Figure 9
100.1
Room-temperature
Mossbauer
spectrum of
feldspar from the Bushveld
Complex. Although this
sample has <0.1 wt% FeO,
data of the quality shown
here have been consistently
acquired with use of a hot
source, large sample size,
and long run time along
with modern
instrumentation.
100.0

Absorption (%)
99.9
99.8
99.7
Bushveld
plagioclase
B25 295K
99.6
99.5
99.4
99.3
99.2
99.1
-4
-3
-2
-1
Velocity (mm/s)
these data demonstrate that it is possible to obtain high-quality Mossbauer

data even
on samples with very low Fe contents. Mossbauer

determinations of Fe3+ /
Fe of plagioclase separates from the Roossenekal proles are providing direct constraints on
the changes in oxygen fugacity of the magmas from which the PM cumulate sequence
crystallized.
The lead author has long been collaborating with Charles Guidotti at the University of Maine to study the chemistry of western Maine metapelites within a petrologic
framework. Our joint studies have focused on the changes in Fe valence and site occupancy in minerals in metapelites over a range of temperatures and f O2 conditions.
We are working with a well-characterized suite of metapelites from lower garnet zone
up to K-feldspar + sillimanite zone conditions with a range of mineral assemblages
representing f O2 from graphite/ilmenite to magnetite-hematite-bearing rocks. To
date, we have studied biotite (Guidotti & Dyar 1991), staurolite (Dyar et al. 2002),
and muscovite (Guidotti et al. 1994) in these rocks, but Mossbauer

analysis of chlorites from Guidotti et al. (1994) has long been stymied by the difculty of obtaining
large quantities of pure mineral separates. The task of handpicking the ne-grained
chlorites from these rocks (at a rate of approximately 1 mg/h) made it difcult to get
the 200 mg of sample previously needed to obtain good quality Mossbauer

data. Although the old samples were too small in mass to give good results in 1991, their 730
mg masses are now more than sufcient to obtain excellent quality Mossbauer
data
with current instrumentation. A spectrum of a 7 mg chlorite is shown in Figure 10.
Preliminary data from samples in this suite suggest that chlorite contains roughly
25% of the total Fe as Fe3+ , independent of metamorphic grade. Further work will
evaluate the effect of changing oxide assemblage on Fe3+ in chlorite. This study il
lustrates the current capability of Mossbauer
spectroscopy to study samples that can
be easily handpicked.
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Figure 10
WF: weak ferromagnet

AF: antiferromagnet
TM : Morin transition
114
100.0
99.8
Absorption (%)
Room-temperature
Mossbauer
spectrum of
chlorite from western
Maine. The sample was t
using quadrupole splitting
distributions; the gure
shows three Fe2+
subcomponents (blue) and
two Fe3+ components (red),
along with a minor ilmenite
impurity (orange). The sum
of the tted components is
shown in green. This
chlorite was handpicked
from a ne-grained
metamorphic rock; the
mount contained 7 mg of
sample.
99.6
99.4
Western Maine
chlorite
CG/BG-6 295K
99.2
99.0
98.8
98.6
98.4
98.2
98.0
97.8
-4
-3
-2
-1
Velocity (mm/s)
A nal example of innovative use of MS can be shown using a comparison of
ILEEMS (which makes measurements at a few-nanometer depths) and conventional
transmission data on hematite, -Fe2 O3 , as described in DeGrave et al. (2005). To
explain this example, it is necessary to understand the magnetic characteristics of
hematite. At temperatures above 265 K (for the pure, well-crystalline endmember),
hematite is a weak ferromagnet (WF). Electron spins in adjacent sites will align
nearly perpendicular to the c axis, with a small canting along that axis. The weak
ferromagnetism is a result of the summing of the spin components along the c axis,
all of which are parallel to each other. As a result, hematite takes on its own weak
magnetization.
Below 265K, Fe3+ atoms in adjacent sites have exactly equal and opposite magnetic moments. In this case, the moments cancel out perfectly, and the material will
have no magnetic moment. The atomic magnetic moment changes direction to become parallel to the c axis (spin op), and the hematite becomes an antiferromagnet
(AF). In hematite, this change is usually designated as the Morin transition, TM (Morin
1950, Morrish 1994).
Variable temperature measurements by MS can be used to distinguish between the
ferromagnetic and AF states because each gives rise to a sextet with its own distinctive
hyperne eld and quadrupole splitting. Such studies have been used to show that
TM decreases in hematites with small particle sizes and poorer crystallinities, and that
substitution of other elements such as Al for Fe3+ also lowers TM (see, e.g., DeGrave
et al. 1988). At temperatures close to TM , contributions from both the WF and the
AF spin states are present in Mossbauer

spectra. DeGrave et al. (1988) suggested that
such coexisting spin states might be explained if the surfaces of the hematite particles
undergo the Morin transition at a different temperature than the interiors of the
Dyar et al.
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crystals. Subsequent work (Vandenberge et al. 2001) has suggested that intermediate
spin states might occur as part of the spin op.
To address this issue, DeGrave et al. (2005) collected ILEEMS and conventional
Mossbauer
spectra of two hematites: one with the endmember -Fe2 O3 composition
and one with a small amount of Al substitution for Fe (-Fe1.87 Al0.13 O3 ). As shown
in Figure 11, each spectrum has been tted with two sextets corresponding to the
Emission (%)
108
-Fe2O3
180K
108
-Fe1.87Al0.13O3
130K
106
106
104
104
102
102
100
100
98
97
96
94
94
Velocity (mm/s)
10
10
Velocity (mm/s)
Figure 11
Mossbauer
spectra of hematite, -Fe2 O3 (left top and bottom) and Al-substituted hematite,
-Fe0.935 Al0.065 O3 (right top and bottom) acquired using the surface technique of ILEEMS (top
set, emission) and conventional transmission Mossbauer,

which samples the bulk mineral.
Adapted from gure 8 in DeGrave et al. (2005). Only the positive velocity half of each
spectrum is shown for simplicity. Each spectrum contains two sextets: one corresponding to an
antiferromagnetic (AF, shaded blue, T < TM , QS > 0) spin state, and one to a weakly
ferromagnetic state (WF, T > TM , QS < 0). In the pure hematite, the spectrum of the surface
is nearly the same as the bulk sample; both contain comparable amounts of WF and AF iron.
In the Al-substituted sample, the WF sextet dominates the ILEEMS (surface emission)
measurement, indicating that the bulk of the Fe at the surface is already above the Morin
transition. In the bulk transmission measurement of the same sample, the WF and AF sextets
are of similar areas. There appear to be two values for TM in the sample, roughly half of the
sample having one value, the other half another value. The temperature of the sample lies
between these two values.
115
91
Transmission (%)
Transmission (%)
100
100
92
Emission (%)

110
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WF (unshaded red lines, QS < 0) and the AF (shaded blue lines, QS > 0) contributions. In the pure (albeit small crystalline) hematite, the spectrum of the surface
is roughly the same as the bulk sample; both contain comparable amounts of WF
and AF iron, with WF somewhat enhanced in the surface as compared with the bulk
sample.
In the Al-substituted sample, the emission and transmission spectra are dramatically different. In the surface (ILEEMS) measurement, the WF sextet (red) is far
more intense than the AF sextet (shaded blue), while in the transmission data, both
sextets are again comparable in intensity. These and related measurements at varying
temperatures suggest that TM is signicantly lowered in the top monolayers of the
hematites. One partial interpretation of this result is that the surface layers may be
richer in Al than the interiors (DeGrave et al. 2005); work is ongoing in that research
group to further explore these results. This study exemplies the potential of surface
Mossbauer
measurements to add greatly to our understanding of redox processes that
occur in the outermost layers of minerals.

ANRV273-EA34-04
PREPARING FOR THE NEXT 50 YEARS

To prepare this eld for important geological studies over the next 50 years (and
beyond!), two important issues need to continue to be addressed. The rst is the
determination of the fundamental Mossbauer

parameters of commonly occurring
rock-forming minerals: the intrinsic isomer shift, I , the characteristic Mossbauer

temperature, M , and the recoil-free fraction, f . These factors are analogous to matrixcorrection effects utilized in electron microscopy in that they are used to convert peak
area ratios determined spectroscopically into valid estimates of actual species concen
trations. Robust application of Mossbauer
spectroscopy to geoscience problems will
require that these parameters be known over a broad compositional range in the
major rock-forming mineral groups.
The second task follows from the rst: The need to evaluate current physical
models and computer algorithms for tting Mossbauer

data, and to compare their
results to true valence state and site occupancies as determined by wet chemistry
and single crystal X-ray diffraction, respectively. Variations in results from tting
procedures among different laboratories are as yet largely undocumented, although
our preliminary work suggests signicant discrepancies in spectral parameters de
termined from the commonly employed tting routines. Mossbauer
spectroscopists
need to be able to reliably compare results from different research groups, and also
to make informed choices for using software that that is most appropriate for their
data.
By addressing these issues, we will effectively reduce the error bars on studies
of Fe using Mossbauer
spectroscopy, increase understanding of tting models and
algorithms, and expand the application of Mossbauer

spectroscopy to an even larger
range of studies of geologic materials.
116
Dyar et al.
ANRV273-EA34-04
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SUMMARY POINTS
1. Since the early 1960s, Mossbauer

spectroscopy in the geosciences has been
predominantly used to study the valence state and coordination of Fe atoms.

2. Mossbauer
spectroscopy is based on the concept of resonant absorption of
nuclear gamma-rays in solids.
3. Mossbauer
parameters include isomer shift (IS), which reects the selectronic charge density at the nucleus; quadrupole splitting (QS), which
arises from a distribution of surrounding charges with less than cubic symmetry; and the magnetic hyperne eld (Bhf ), which indicates magnetic order
or an externally applied eld.
4. IS, QS, and Bhf vary fairly systematically with the valence state (Fe0 , Fe2+ ,
Fe3+ ) and coordination number (generally 4- to 8-coordination) of Fe. Because rules for atomic radius ratios predict that Fe3+ will most commonly
occur in 4- or 6-coordination with oxygen, and Fe2+ in 6-coordination,
many minerals have the same or quite similar Mossbauer

parameters. Thus,
Mossbauer
parameters are generally not sufciently diagnostic for mineral
identication.
5. Mossbauer
instrumentation now includes many variations, such as transmission, backscatter, milliprobe, CEMS, and integral low-energy electron
Mossbauer
spectroscopy (ILEEMS). The technique is now routinely used
for the study of very small Fe-rich geological samples (110 mg), as well as
larger amounts of low-Fe samples such as feldspar.
6. Interpretation of Mossbauer
lineshapes is quite complex, and software available for analysis uses a variety of physical models. Fits using different models
may produce highly variable results.
7. Recoil-free fraction ( f ), which is a measure of the rigidity of the bonds
surrounding the Fe atom, is the most important factor that must be known
to relate the peak areas in a Mossbauer

spectrum to the actual abundances
of the represented species.
8. Future work in this eld must address the variation of f with mineral composition and structure and resolve differences in interpretation that arise
from use of different tting models.
ACKNOWLEDGMENTS
This work was supported by NASA grants NAG5-12687 and NNG04GG12G and
NSF grants EAR-0439161 and EAR-0439077. We thank Tom Kent for contributions
to the instrumentation section; Kylie Hanify and Yarrow Rothstein for help with
citations; and Eddy DeGrave for preprints, thoughtful discussions, and use of gures
from works in progress.
117
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Excellent, up-to-date
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materials found in Earths
crust, as well as their
synthetic analogs and
industrial processing.
123
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Description of application
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data,
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125
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Contents
Annual Review
of Earth and
Planetary
Sciences

Volume 34, 2006
Threads: A Life in Geochemistry

Karl K. Turekian p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p 1
Reections on the Conception, Birth, and Childhood of Numerical
Weather Prediction
Edward N. Lorenz p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p37
Binary Minor Planets
Derek C. Richardson and Kevin J. Walsh p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p47
Mssbauer Spectroscopy of Earth and Planetary Materials
M. Darby Dyar, David G. Agresti, Martha W. Schaefer, Christopher A. Grant,
and Elizabeth C. Sklute p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p83
Phanerozoic Biodiversity Mass Extinctions
Richard K. Bambach p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p 127
The Yarkovsky and YORP Effects: Implications for Asteroid Dynamics
William F. Bottke, Jr., David Vokrouhlicky, David P. Rubincam,
and David Nesvorny p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p 157
Planetesimals to Brown Dwarfs: What is a Planet?
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History and Applications of Mass-Independent Isotope Effects
Mark H. Thiemens p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p 217
Seismic Triggering of Eruptions in the Far Field: Volcanoes and
Geysers
Michael Manga and Emily Brodsky p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p 263
Dynamics of Lake Eruptions and Possible Ocean Eruptions
Youxue Zhang and George W. Kling p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p 293
Bed Material Transport and the Morphology of Alluvial River Channels
Michael Church p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p 325
Explaining the Cambrian Explosion of Animals
Charles R. Marshall p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p 355
vii
Contents
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Cosmic Dust Collection in Aerogel

Mark J. Burchell, Giles Graham, and Anton Kearsley p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p 385
Using Thermochronology to Understand Orogenic Erosion
Peter W. Reiners and Mark T. Brandon p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p 419
High-Mg Andesites in the Setouchi Volcanic Belt, Southwestern Japan:
Analogy to Archean Magmatism and Continental Crust Formation?
Yoshiyuki Tatsumi p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p 467

Hydrogen Isotopic (D/H) Composition of Organic Matter During

Diagenesis and Thermal Maturation
Arndt Schimmelmann, Alex L. Sessions, and Maria Mastalerz p p p p p p p p p p p p p p p p p p p p p p p p p p 501
The Importance of Secondary Cratering to Age Constraints on
Planetary Surfaces
Alfred S. McEwen and Edward B. Bierhaus p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p 535
Dates and Rates: Temporal Resolution in the Deep Time Stratigraphic
Record
Douglas H. Erwin p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p 569
Evidence for Aseismic Deformation Rate Changes Prior to
Earthquakes
Evelyn A. Roeloffs p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p 591
Water, Melting, and the Deep Earth H2 O Cycle
Marc M. Hirschmann p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p 629
The General Circulation of the Atmosphere
Tapio Schneider p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p 655
INDEXES
Subject Index p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p 689
Cumulative Index of Contributing Authors, Volumes 2434 p p p p p p p p p p p p p p p p p p p p p p p p p p p 707
Cumulative Index of Chapter Titles, Volumes 2434 p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p 710
ERRATA
An online log of corrections to Annual Review of Earth and Planetary Sciences
chapters may be found at http://earth.annualreviews.org
viii
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ANRV273-EA34-04

Annu. Rev. Earth Planet. Sci. 2006.34:83-125. Downloaded from www.annualreviews.org

Department of Physics, University of Alabama at Birmingham, Birmingham, Alabama 35294-1170;

Annu. Rev. Earth Planet. Sci.

Department of Chemistry, University of Oregon, Eugene, Oregon 97401

The eld of Mossbauer

Annu. Rev. Earth Planet. Sci. 2006.34:83-125. Downloaded from www.annualreviews.org

XANES: X-ray absorption

The technique of Mossbauer

2002a). Milliprobe Mossbauer

common rock-forming minerals by Bancroft and Burns within 10 years of Mossbauers

to grow, with generally more than 100 studies of the Mossbauer

physics behind the Mossbauer

HOW THE MOSSBAUER

Annu. Rev. Earth Planet. Sci. 2006.34:83-125. Downloaded from www.annualreviews.org

Fundamentals of Resonant Absorption

Recoilless nuclear resonance was discovered by Mossbauer

www.annualreviews.org Mossbauer Spectroscopy

Annu. Rev. Earth Planet. Sci. 2006.34:83-125. Downloaded from www.annualreviews.org

by an isolated atom at rest in a nuclear transition of energy E0 must possess an

In principle, the resonance process could occur if v were sufciently large (4

Annu. Rev. Earth Planet. Sci. 2006.34:83-125. Downloaded from www.annualreviews.org

is the absolute temperature. At room temperature, T 300 K and k B T 0.025 eV,

zero at the lowest temperatures. This is what Mossbauer

expectations, the absorption increased dramatically (Mossbauer

Because a correct theoretical treatment (e.g., Mossbauer

where n = 0, 1, 2, . . . is the vibrational quantum number, or the number of phonons

www.annualreviews.org M&ouml;ssbauer Spectroscopy

Annu. Rev. Earth Planet. Sci. 2006.34:83-125. Downloaded from www.annualreviews.org

Clearly, larger values of f are desirable. Thus, the Mossbauer

Finally, the Mossbauer

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What is it that makes 57 Fe special? In principle, the Mossbauer

accomplished. The vast majority of Mossbauer

Conversion electron Mossbauer

www.annualreviews.org Mossbauer Spectroscopy

Annu. Rev. Earth Planet. Sci. 2006.34:83-125. Downloaded from www.annualreviews.org

KLL 5.4 keV

14.4 keV -rays

Depth-selective conversion electron Mossbauer

Integral low-energy electron Mossbauer

for studies of mineral surfaces (Klingelhofer

Simultaneous gamma, X-ray, and electron Mossbauer

Annu. Rev. Earth Planet. Sci. 2006.34:83-125. Downloaded from www.annualreviews.org

What makes Mossbauer

different, diagnostic energies. A typical Mossbauer

www.annualreviews.org Mossbauer Spectroscopy

Annu. Rev. Earth Planet. Sci. 2006.34:83-125. Downloaded from www.annualreviews.org

Isomer shift (IS): shift up

iron nucleus in a specic environment in the sample (a Fe nuclear site). Different

Annu. Rev. Earth Planet. Sci. 2006.34:83-125. Downloaded from www.annualreviews.org

denoted by IS or (Figure 5, blue). The shift results from a Coulombic interaction

correct for minerals, the resultant Mossbauer

www.annualreviews.org Mossbauer Spectroscopy

Bhf = Eg 8.416 T(mm/s)1 , where g = 0.181208(9) and N = 3.1525 108

Annu. Rev. Earth Planet. Sci. 2006.34:83-125. Downloaded from www.annualreviews.org

available to the geological community. Exact values of Mossbauer

effects of covalent bonding. Variations in Mossbauer

(Table 1). Furthermore, most minerals exhibit a range of Mossbauer

discussion of f below). For these reasons, Mossbauer

Isomer shift (mm/s)

Isomer shift (mm/s)

Annu. Rev. Earth Planet. Sci. 2006.34:83-125. Downloaded from www.annualreviews.org

www.annualreviews.org Mössbauer Spectroscopy

Bhf = Eg 8.416 T(mm/s)1 , where g = 0.181208(9) and N = 3.1525 108