Article

pubs.acs.org/est

Direct Observation of Tetrahedrally Coordinated Fe(III) in

Ferrihydrite
Derek Peak†,* and Tom Regier‡
†
Department of Soil Science, College of Agriculture and Bioresources, University of Saskatchewan, 51 Campus Drive, Saskatoon,
Saskatchewan, Canada S7N 5A8
‡
Canadian Light Source, Inc., 101 Perimeter Road, Saskatoon, Saskatchewan, Canada, S7N 0X4
*
S Supporting Information

ABSTRACT: Ferrihydrite is a common iron hydroxide

nanomineral commonly found in soils, sediments, and surface
waters. Reactivity with this important environmental surface
often controls the fate and mobility of both essential nutrients
and inorganic contaminants. Despite the critical role of
ferrihydrite in environmental geochemistry, its structure is
still debated. In this work, we apply bulk sensitive Fe L edge X-
ray absorption spectroscopy to study the crystal field
environment of the Fe in ferrihydrite and other Fe oxides of
known structure. This direct probe of the local electronic
structure provides verification of the presence of tetrahedrally
coordinated Fe(III) in the structure of ferrihydrite and puts to
rest the controversy on this issue.

■ INTRODUCTION
Ferrihydrite is the initial solid product of Fe(III) hydrolysis in
solution, and is the precursor to more crystalline forms of iron
oxides.1 However, ferrihydrite is metastable in natural systems
and persists both as discrete particles and as surface coatings in
soils and sediments. Its large surface area and functional group
density2 make it an important sorbent for nutrients3,4 and
contaminants5−7 and it is also a common iron(III) source for
iron reducing bacteria.8
Contaminant reactivity is often controlled by sorption
reactions at the mineral/water interface. Accordingly, geo-
chemical transport modeling relies upon surface complexation
theory to describe the interfacial chemistry with functional
groups and sorption reactions at the solid/water interface. To
refine these models and improve their predictive ability, it is
important to understand the structure of nanominerals such as
ferrihydrite.
For over two decades, the structure of synthetic ferrihydrite
has been extensively studied by many scientists using a range of
spectroscopic techniques including Mössbauer,9−11 EELS,12
XANES,13−18 EXAFS,19,20 and PDF/X-ray scattering.21,22
Rather than conclusively providing a model of the short-
range ordered material, the intense investigation of ferrihydrite
has instead produced two competing structural models: one in
which tetrahedral Fe is an important structural component, and
a second in which only octahedral ferric iron is present.
Although a ferrihydrite structural model which contained
tetrahedral Fe was first proposed in 1988, the strongest
evidence for tetrahedral Fe in ferrihydrite comes from recent
studies using PDF and XAS. In a 2007 study, Michel and co-
workers21 reported a single-domain model for ferrihydrite
containing both tetrahedral and octahedral iron. This model
was developed by calculating a pair distribution function (PDF)
from the reduced structure function obtained via synchrotron-
based X-ray total scattering data. They later revised their
structural model slightly22 but the overall structure proposed is
that of a 13 Fe unit where 12 Fe are octahedral and a central Fe
is tetrahedral. This building block is iso-structural with the
extensively studied Al13 soluble complex.23 Recent high quality
XANES18 and EXAFS18,20 experiments are generally supportive
of the model proposed by Michel and colleagues, with some
disagreement on the amount of tetrahedral Fe that is present in
the structure.
This model stands in contrast to a competing multiple
domain octahedral Fe structural model of ferrihydrite first
proposed by Drits and co-workers in 1993.24 In this model,
ferrihydrite is a mixture of two major components: a d-phase
that is feroxyhite-like and an f-phase that is akaganeite/goethite
like in structure. Recently, Manceau has evaluated the quality of
this model and reanalyzed PDF and XAS measurements of
other researchers25−27 and concluded it is the best model to
describe all of the existing XANES, EXAFS, and scattering
results.
One reason for the contradictory structural models is that (a)
many of the chosen spectroscopic techniques produce
Received: July 23, 2011
Revised: February 8, 2012
Accepted: February 27, 2012
Published: February 27, 2012

© 2012 American Chemical Society 3163 dx.doi.org/10.1021/es203816x | Environ. Sci. Technol. 2012, 46, 3163−3168
Environmental Science & Technology
ambiguous results when used to probe the ferrihydrite structure
and (b) the concentration of tetrahedral Fe may be close to the
limits of detection for the method. Pre-edge features consistent
with tetrahedral Fe are seen in Fe K-edge XANES spectra of
ferrihydrite,13,18 but a plausible alternative explanation for the
features that only involves octahedral Fe(III) has also been
made.14,16 Mössbauer measurements have been utilized as
proof that ferrihydrite only contains octahedral Fe(III) by the
Drits model but were also used to set an upper-limit of
tetrahedral Fe(III) in the Michel model. EXAFS is commonly
employed for structural studies of short-range order materials,
but EXAFS provides an average local environment, and
ferrihydrite EXAFS studies have similarly been contradictory.
In the case of ferrihydrite, overlap in the interatomic distances
of tetrahedral iron sites and some octahedral linkages are a
challenge for EXAFS to resolve; nonetheless recent studies
using high-k, high-resolution data developed a model including
tetrahedral iron to fit their ferrihydrite.20 However, it has been
argued by Manceau27 that these results are over fit, and that the
Drits model can acceptably explain the EXAFS results of ref 20
without including tetrahedral Fe.
Fe L-edge XANES of ferrihydrite probes the local electronic
structure at the Fe sites in bulk and nanocrystalline samples
with great sensitivity, and presents a possible alternative to K-
edge experiments. The L-edge XANES provides different
information on the Fe crystal environment than does Fe K-edge
XANES because of the allowed dipole transitions for 1s vs 2p
electrons. K edge spectra reflect the density of unoccupied 2p
states, commonly associated with the unoccupied O 2p orbitals
in the iron oxides, while L edge spectra involve excitation into
the unoccupied 3d states of Fe. The effect of the crystal field on
these orbitals is to remove their degeneracy, introducing a fine
structure in the absorption spectrum that is highly specific to
the site symmetry. EELS at the Fe L-edge has been successfully
used to probe the electronic structure of ferrihydrite12 but low
energy resolution and increased beam damage to samples in
EELS measurements make the approach less than ideal.
Synchrotron-based L-edge XANES provides information
similar to EELS, but with a much lower radiation dose and
increased spectral resolution (0.1 eV vs 1 eV).
Despite the utility of Fe L-edge XANES for studies of the
structure of the iron oxides, the technique has, until now, not
been specifically applied for this purpose. The primary reason
for this is due to the lack of a suitable detection technique.
Total electron yield (TEY) measurements are highly surface
sensitive and will be heavily influenced by the surface oxidation
or surface contamination of the samples. Fluorescence yield
techniques on concentrated samples are bulk sensitive but may
not be useful because of saturation effects.28 Total fluorescence
measurements at the Fe L-edge are also susceptible to
nonlinear backgrounds arising from the energy dependence in
the O K emission.29 Scanning transmission X-ray microscopy
(STXM) is one suitable method for the study of nano-
structured compounds, where a suitable optical contrast exists.
But many of the relevant reference materials for ferrihydrite
may not readily exist at the size scale necessary for STXM
analysis, making comparison with standards problematic.
The above technical problems related to XANES measure-
ment have resulted in only a limited application of Fe L-edge
XANES for studies of bulk materials. In a recent study the TEY
method was used to probe the surface structure Fe L-edge of
ferrihydrite-silicate solids subjected to calcining.30 STXM
studies on two and six line ferrihydrite have shown that
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significant amount of octahedral Fe3+ exist in the structure but a
detailed comparison with all relevant reference compounds is
not used in these studies.31,32 In particular, Pan and
collaborators interpret their six line ferrihydrite STXM data
to be representative of Fe3+ in octahedral co-ordination but do
not compare their measurements to that of maghemite which is
known to contain tetrahedral Fe3+.33
In this study, we apply a recently developed fluorescence
measurement method called inverse partial fluorescence yield
(IPFY), which is bulk sensitive and free of self-absorption
effects34 to measure the Fe L-edge XANES of several iron
(hydr)oxides. The results of these bulk sensitive measurements,
when compared to the surface sensitive TEY measurements,
confirm the presence of tetrahedral Fe(III) in the structure of
synthetic 2 line ferrihydrite.
■ MATERIALS AND METHODS
Synthetic commercial hematite, magnetite, wü stite, and
maghemite were purchased from Alfa Aesar and Sigma Aldrich,
and a synthetic goethite, akaganeite, and ferrihydrite (2-line)
were synthesized using the methods of ref 1 with the following
modifications. For goethite synthesis, the initial hydrolysis
product was aged at 298K for 14 days and prior to freeze-drying
was acid washed in 0.4 M HCl to remove residual amorphous
Fe(OH)3. The resulting product consisted of 100 nm rods that
had BET surface area of 65 m2g−1. For ferrihydrite a solution of
1 M Fe(Cl)3 was neutralized with 1 M KOH under N2 sparging
and continuous stirring: the resulting suspension was held at
pH 7.5 for one hour using a computer-controlled titrator
(Metrohm 718) and then washed via centrifugation 3 times
with 0.1 M NaCl to remove entrained and adsorbed Fe3+ and
Cl− and then 5 times with 18 MΩ H2O (Barnstead Diamond
NanoPure) to remove soluble salts prior to flash freezing in
N2(l) and freeze-drying.
XANES measurements were performed at the Spherical
Grating Monochromator (SGM) beamline of the Canadian
Light Source in Saskatoon, SK. Dry samples were prepared by
placing a small amount of homogenized (via agate mortar and
pestle) powder on graphite tape. All samples were scanned
from 700 to 735 eV in 0.1 eV steps, which encompasses both
the Fe L2 and L3 absorption edges. Surface sensitive absorption
spectra were recorded using TEY and bulk sensitive absorption
spectra were measured using IPFY. TEY employs the intensity
of emitted secondary electrons as a probe of the attenuation
coefficient. At normal incidence, TEY is not susceptible to
saturation effects because the attenuation length of the
electrons is much shorter than the attenuation length of the
incident photons. However, this also implies that TEY is only a
probe of the surface (∼5 nm) of the solid rather than the bulk
structure. To probe the bulk structure, IPFY measurements
were made using an energy resolving fluorescence yield
detector to monitor the intensity of the O Kα emission as the
incident photon energy was scanned across the Fe L2 and L3
absorption threshold. For these experiments, a commercial
silicon drift detector (SDD) with an energy resolution of ∼150
eV was used. IPFY was then calculated by taking the inverse of
the O PFY after normalization to the incident photon flux as
recorded by a gold mesh.
To illustrate the IPFY technique and its advantages, Figure 1
shows the results from analysis of the synthetic ferrihydrite
sample at the Fe L-Edge. In the upper portion of the figure, the
excitation−emission matrix is presented. Two regions show
significant fluorescence when the sample is scanned through
dx.doi.org/10.1021/es203816x | Environ. Sci. Technol. 2012, 46, 3163−3168
Environmental Science & Technology
Figure 1. Fe L-Edge XANES spectrum of ferrihydrite. At top is the
excitation−emission matrix for the sample that has been normalized to
the incident flux. The middle portion contains the total fluorescence
(obtained by averaging the total emission at each energy) as well as the
partial fluorescence arising from either Fe or O emission. At bottom is
the IPFY spectrum, which represents the bulk Fe L-Edge free from
self-absorption effects.
the Fe L2,3 edges: these correspond to Fe Lα and Lβ emission
(625−725 eV) and O Kα emission (450−550 eV). Total
fluorescence (TFY) is produced simply as the sum of all
fluorescence at that excitation energy (Fe + O for ferrihydrite),
and is analogous to the signal from commonly used total
fluorescence detectors such as micro channel plates or diodes.
The ability to separate the individual elemental contributions to
the total fluorescence reveals that the energy dependence in the
total signal arises not only from increasing Fe fluorescence, but
instead from a strong decrease in the O Kα emission. As a
consequence of this, significant distortion in the TFY occurs,
including a sub-background absorbance in the Fe edge due to
the decrease in the O emission being larger than the increase in
Fe emission.34 The lower portion of Figure 1 shows the inverse
of the normalized O fluorescence, which is proportional to the
total attenuation coefficient of the material.34 The inverse of the
partial fluorescence yield of the O in the sample therefore
provides access to a high quality fluorescence spectrum of Fe
that is free from self-absorption effects present in Fe PFY.
■ RESULTS AND DISCUSSION
In Figure 2, we combine the TEY (surface) and IPFY (bulk)
spectra of goethite (α-FeOOH), akaganeite (β-FeOOH)
hematite (α-Fe 2 O 3 ), maghemite (γ-Fe 2 O 3 ), magnetite
(Fe3O4), and wüstite (FeO) standards with the TEY and
IPFY of ferrihydrite. These standards were chosen to provide a
spectral reference for both octahedrally and tetrahedrally
coordinated Fe(III) as well as octahedral Fe(II). In goethite,
hematite, and akaganeite all of the iron is octahedrally
coordinated Fe(III). Maghemite contains both tetrahedral and
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Figure 2. Fe L-Edge XANES of a variety of mineral samples compared
with ferrihydrite. The surface spectra are denoted by TEY (dashed
line), whereas the bulk spectra are IPFY (solid lines).
octahedral Fe(III) in a spinel ferrite structure. In magnetite,
one-third of the Fe sites are octahedral Fe(II), one-third are
octahedral Fe(III) and the remaining third are octahedral
Fe(III). Ferrous oxide contains only octahedrally coordinated
Fe(II).
It has been established via both experiment and theoretical
calculations35 that Fe L-edge XAS spectra are dominated by the
dipole-allowed 2p-3d transitions. Two major spectral features
are observed in Fe XANES of these minerals. First of all, the Fe
L-edge of all samples are well resolved into separate L3 (706−
713 eV) and L2 (718−725 eV) regions as a result of spin−orbit
coupling. Second, there is additional splitting of these main
peaks that occurs due to the electronic interaction between the
Fe 3d and the O 2p orbitals. Specifically, the degeneracy
between the 5 different Fe d orbitals is lifted, giving rise to the
eg and t2 g orbitals with a splitting that is highly sensitive to the
coordination environment.
In goethite, akaganeite, and hematite, there is pronounced
splitting of the L3 edge into two well-resolved peaks at
approximately 708.1 and 709.5 eV. This is consistent with
octahedral Fe(III) being the only coordination environment.
The close agreement between the surface sensitive TEY and
bulk sensitive IPFY suggests that there is little or no difference
between the Fe coordination at the surface and the bulk of
these materials. A slight shift (∼0.1 eV) to higher energy
position for goethite relative to hematite occurs for the main L3
peak. This has not been reported in the literature due to the
lack of high resolution XANES, but it can be reasonably
explained from crystal field theory. Hematite is red, whereas
goethite is ochrous, which is evidence of a slightly decreased
dx.doi.org/10.1021/es203816x | Environ. Sci. Technol. 2012, 46, 3163−3168
Environmental Science & Technology Article

crystal field splitting (distance between the 2 observed L3 important information about the iron coordination in this
peaks). An important point to make about these crystalline nanomineral. First of all, the splitting of the L3 peak into two
octahedral minerals is that, while the Fe−O bond distances and peaks with the same energies as hematite, goethite, and
angles vary tremendously in these two crystal structures, the L- maghemite provides unsurprising validation of Fe(III) in this
edge XANES splitting remains sharp and well resolved in both iron hydroxide. Also of note is that the surface and bulk
spectra. At the K-edge, it has been reported that ferrihydrite XANES of ferrihydrite are quite similar, suggesting that the
and akaganeite are indistinguishable; their L-edge spectra are same coordination of Fe exists in the surface and in the bulk of
quite different. This highlights the fact that L-edge absorption this material. More importantly, the relative intensities and the
spectroscopy is much more sensitive to the average crystal field relatively poor resolution of the splitting between the 2 bands
environment in materials than it is to specific bond lengths and of the L3 peak is clear evidence of the presence of Fe(III) in
angles. The latter are more aptly probed by measuring the more than one configuration. This point is emphasized when
EXAFS above the K-edge, which is sensitive to photoelectron ferrihydrite is plotted on top of maghemite, as shown in Figure
scattering pathways. 3. Indeed, the similarity between ferrihydrite and maghemite
In contrast to ferric oxides and hydroxides, the fluorescence
yield spectra of wüstite and magnetite differ significantly from
their electron yield spectra, which is the result of strong surface
modification in the Fe(II) containing samples. The bulk spectra
for both minerals are dominated by a large broad peak at 709
eV that has a low energy shoulder at 706.5 eV. An additional
shoulder is observed in the magnetite spectra at 708 eV. The
spectral shapes are consistent with previous theoretical models
of wüstite as an octahedral Fe(II) compound36 and magnetite
as a mixed valence compound with Fe(II) and Fe(III) in
octahedral sites and Fe(III) in a tetrahedral site.37 The low
energy shoulders can be used as clear indicators of the presence
of Fe(II) in the bulk of the samples.38 The electron yield
spectra of the Fe(II)-containing compounds show some
splitting in the L3, but it is not as well resolved as in hematite
and goethite. For wüstite, there is a shift of the position of the
L3 peaks to higher energy when compared to the bulk
suggesting that the surface iron has been largely converted to
octahedral Fe(III). But the persistence of the shoulder at 706.5
eV in the electron yield data demonstrates that some octahedral
Fe(II) is present at or near the surface. The differences in the
electron yield and fluorescence yield can readily be explained by
the surface oxidation of wüstite from octahedral Fe(II) to
tetrahedral Fe(III). Indeed, wüstite is well-known to partially
oxidize and form tetrahedral Fe(III) and tetrahedral Fe(III) is
required to refine the crystal structure of wüstite.36 This
oxidation would be expected to occur preferentially on the
surface of the material. Our results suggest that a similar surface
modification is occurring for magnetite.
Maghemite is a polymorph of the purely octahedral hematite Figure 3. Fe L3-Edge XANES bulk spectra of minerals compared to
that contains 20−33% tetrahedral Fe(III) depending upon site ferrihydrite.
vacancies.33 The spectrum of maghemite differs from that of
hematite in that the L3 peak is noticeably broader, resulting in a can only be readily explained by the presence of tetrahedral
less well resolved splitting. The broadening has previously been Fe(III) in ferrihydrite. It is also possible to estimate the relative
modeled35 and assigned to a combination of the distortion of percentages of octahedral and tetrahedral iron via fitting the
the symmetry of the Fe(III) octahedra and the presence of a IPFY data for maghemite and ferrihydrite with theoretical
second Fe(III) tetrahedral component with a reduced crystal tetrahedral and octahedral sites obtained from the literature.35
field splitting. This tetrahedral Fe(III) is predicted to have a
The fitting produced results (Supporting Information, SI)
main peak position slightly lower than octahedral Fe(III),
suggest that 30−40% tetrahedral Fe is present in both mineral
which causes the maghemite L3 to broaden. Since the ligand
field splitting remained well resolved in the highly disordered phases. This is somewhat higher than the 10−12% tetrahedral
akaganeite standard, it is unlikely that disorder alone can Fe in ferrihydrite proposed based upon PDF calculations22 and
account for the observed broadening in ferrihydrite. There is Fe K-edge XANES,18 but agrees reasonably well with the values
little difference between the surface and bulk spectra of this proposed by Maillot et al.20 obtained via EXAFS. It must be
mineral, which shows that, in contrast to wüstite, tetrahedral noted that the molar absorptivity for octahedral and tetrahedral
iron is present throughout the structure of the mineral rather Fe3+ was assumed to be identical in the above relative %
than only on the surface. calculations; this may overestimate the true tetrahedral amount
Given the above discussion about the surface and the bulk of if this assumption is false. However, our LC modeling was
the known Fe oxide standards, the spectrum of synthetic extremely sensitive to changing the E0 of the calculated sites; if
ferrihydrite powder, shown in Figure 2, reveals some new and allowed to independently vary, it can produce ∼10% variation
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Environmental Science & Technology
in the tetrahedral component. However, in no case could using
only octahedral sites reproduce the features of the ferrihydrite
L-edge XANES; tetrahedral Fe in 15% or more was always
required to obtain a reasonable fit.
Because researchers had previously shown that electron beam
damage could reduce Fe(III) to Fe(II) in EELS studies of
ferrihydrite,12 we carefully evaluated our XANES results for
photoreduction. This was tested by either collecting multiple
scans on a single spot or by running scans with a reduced beam
flux. We observed no change in the Fe L-Edge XANES of any
of our iron oxide samples. Furthermore, no systematic
difference in TEY vs IPFY is observed in our ferrihydrite
samples that would be consistent with reduction occurring over
the course of the measurements. Finally, if photoreduction were
occurring to a large extent on ferrihydrite, then it should also be
detected for goethite and hematite. The hematite and
maghemite spectra match theoretical calculations for Fe2O3 in
the literature very closely,35 which would not be expected if
photoreduction were important. On the basis of the above
evidence, we are confident that tetrahedral Fe(III) is the source
of the observed spectral features of ferrihydrite.
The presence of tetrahedral Fe in ferrihydrite has several
potential effects for contaminant stability and reactivity in soils,
sediments, and engineered systems. It is expected that any
surface functional groups formed at tetrahedral sites would have
stronger bonding with H2O or OH ligands based upon
Pauling’s electrostatic bond strength. This could have effects
such as slowing the rate or extent of ligand exchange between
Fe−OH2+ groups and oxyanions at low pH. This is consistent
with bonding mechanisms observed for ligands such as sulfate39
and selenate40 adsorption on ferrihydrite (predominantly outer-
sphere except below pH 4) and goethite/hematite (inner-
sphere complexes form over a much wider pH range). This
same chemical property (stronger Fe−O bonding in surface
groups) would enhance metal cation bonding on ferrihydrite
tetrahedral sites, since protons of Fe−OH would be more
readily exchanged to form Fe−O−Me inner-sphere complexes.
Of more general importance is the role that tetrahedral iron
might play in the stability of ferrihydrite in natural systems. It
has been shown in synthetic laboratory experiments41 the
transformation of high surface area amorphous Fe(OH)3 into
crystalline goethite and/or hematite has been shown to either
incorporate trace metals into the resulting iron crystal structure
or else release adsorbed metals as surface area decreases. The
active mechanism depends upon solution conditions as well as
the metal present. The presence of tetrahedral iron in
ferrihydrite may play a role in the persistence of this high
surface area mineral as a metastable phase in natural systems.
The consistency between the electron yield and fluorescence
yield spectra of ferrihydrite allows us to additionally conclude
that the tetrahedral Fe(III) is structural. However, in a
nanoparticle such as ferrihydrite, the distinction between
surface and bulk spectra may lose some of its meaning. Many
researchers report less than 10 nm average particle diameter for
ferrihydrite so the electron yield is expected to be sensitive to
the majority of the ferrihydrite particles. It is therefore possible
that the source of tetrahedral Fe(III) in ferrihydrite is the
production of under-coordinated Fe(III) at the surface of dried
samples as a result of the freeze-drying process commonly used
in mineral synthesis. Future L-edge studies of ferrihydrite in
aqueous suspensions should be conducted to verify whether
tetrahedral Fe forms in the synthesis of this material in solution
or instead upon drying. This could elucidate whether there are
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differences between the powder ferrihydrite used for structural
analysis and the initial hydrolysis product in solution often
referred to as hydrous ferric oxide, or HFO.
In conclusion, this Fe L-Edge XANES study provides direct
proof for tetrahedral Fe(III) in the structure of ferrihydrite, and
supports the PDF-based model of Michel that proposed
ferrihydrite is iso-structural with aluminum polymer sys-
tems.21,22 Recent soft X-ray spectroscopic studies at the Al K-
and L-edge have also directly observed that amorphous
aluminum oxides contain tetrahedral Al3+ that converts to
octahedral Al as the minerals crystallize into octahedral
minerals.42,43 This may imply that similar polymerization/
condensation/precipitation mechanisms may be active for both
iron and aluminum. Additionally, the use of the bulk-sensitive
IPFY approach detailed in this work can provide new structural
information on many other amorphous transition metal oxide
and hydroxide phases of environmental importance that are
difficult to differentiate and identify with K-edge XAS or
EXAFS.
■ ASSOCIATED CONTENT
* Supporting Information
S
Additional Fe L-edge XANES of octahedral ferric oxoanion
salts, simulations of L-edge XANES from mixing (a) multiple
octahedral sites or (b) octahedral and tetrahedral sites. This
material is available free of charge via the Internet at http://
pubs.acs.org.
■
AUTHOR INFORMATION
Corresponding Author
*E-mail: derek.peak@usask.ca.
Notes
The authors declare no competing financial interest.
■
ACKNOWLEDGMENTS
The authors would like to thank Robert Green (University of
Saskatchewan) for his helpful comments and suggestions about
L-edge modeling. D.P. acknowledges funding for this research
from the National Sciences and Engineering Research Council
of Canada Discovery grant program. Research described in this
work was performed at the Canadian Light Source, which is
supported by the Natural Sciences and Engineering Research
Council of Canada, the National Research Council of Canada,
the Canadian Institutes of Health Research, the Province of
Saskatchewan, Western Economic Diversification Canada, and
the University of Saskatchewan.
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