DOI: 10.5281/zenodo.11285023
title: Data set from: Can laboratory-based XAFS compete with XRD and Mössbauer spectroscopy as a tool for quantitative species analysis?

description: Abstract: This work investigated the capability of quantitative laboratory X-ray Absorption Fine Structure Spectroscopy (lab-XAFS) via Linear Combination Fitting (LCF) of reference spectra in comparison with quantitative X-ray diffraction (XRD) and Mössbauer spectroscopy. While lab-XAFS already show good results when performing LCF with significant different spectra of the species to be identified, the method is challenging when the reference spectra and possibly species in the sample are very similar as it is the case for α-Fe2O3, γ- Fe2O3 and Fe3O4. For this investigation an iron oxide mineral with origin from Mexico (here named Mexican Magnetite) with different iron oxide phases was used and measured using all three methods.

 

This data set contains the raw data of the work “Can laboratory-based XAFS compete with XRD and Mössbauer spectroscopy as a tool for quantitative species analysis? Critical evaluation using the example of a natural iron ore” of XAFS, XRD and Mössbauer measurements. This includes XAFS, Mössbauer and XRD spectra of the reference materials α-Fe2O3, Fe3O4 and the sample Mexican magnetite, the XAFS spectra of the reference material γ- Fe2O3 and the XAFS, XRD and Mössbauer spectra of three different α-Fe2O3/Fe3O4 mixtures.

 

Sample information/sample list

sample/references: The sample and the corresponding short cut name used in the data files is listed. Furthermore the method the sample was measured with is also listed.






Short cut name



 Sample/reference



Measured with





MexicanMagnetite



 Iron oxide mineral with origin in Mexico



XAFS, XRD, Mössbauer





Fe2O3



Fe2O3-alpha / Hematite



XAFS, XRD, Mössbauer





Fe3O4



Fe3O4 / Magnetite



XAFS, XRD, Mössbauer





Fe



Iron powder



XAFS





Fe2O3-alpha



Fe2O3-alpha / Hematite



XAFS





Fe2O3-gamma



Fe2O3-gamma / Maghemite



XAFS





30-70



Mixture of  30 % Fe2O3-alpha/ 70 %Fe3O4



XAFS, XRD, Mössbauer





50-50



Mixture of  50 % Fe2O3-alpha/ 50 %Fe3O4



XAFS, XRD, Mössbauer





70-30



Mixture of  70 % Fe2O3-alpha/ 30 %Fe3O4



XAFS, XRD, Mössbauer





 

Mixtures ratios: The prepared Fe2O3-Fe3O4 model mixtures with the weight-in ratios and the actual achieved mass percentage ratio between the two iron species, taken impurities of the used materials into account, are listed below. The short cut name is the name used in the data files (see table above).






Short cut name



Actual achieved weigh-in ratios

m(Fe2O3)/m(Fe3O4)*



Actual achieved mass percentage ratios ωrel(Fe2O3) / ωrel(Fe3O4)





30-70



0.31380 g / 0.7059 g



31.8 / 68.2





50-50



0.5140 g / 0.5174 g



50.6 / 49.4





70-30



0.7037 g / 0.3041 g



70.5 / 29.5





*the given masses here, ar the masses of the materials of the mixtures before sampel prepration. For the sample prepration the mass  applied on the tape or mixed with wax is about 5-10 mg.

Spectrometer Specifications

XAFS: The experimental setup for the laboratory XAFS measurement is based on the Highly Annealed Pyrolytic Graphite (HAPG) von Hámos spectrometer with the use of a cylindrically shaped crystal.

As detector unit the pixelated X-ray hybrid-CMOS detector Dectris Eiger2 R 500k was used. The area of detection is 77.3 mm x 38.6 mm with a pixel size of 75 µm x 75 µm. The X-ray source was a water-cooled micro focus X-ray tube with molybdenum as anode material, a power of 30 Watt optimised at 15 kV and a spot size of 70 µm.

Sample preparation: α-Fe2O3, Fe3O4, the three α-Fe2O3/Fe3O4 mixtures and the sample Mexican magnetite were applied on adhesive tape, sliced in 1cm x 1cm pieces characterized with XRF to determine the iron content as [Q] = mg/cm² and then stacked by taking the iron content of each slice into account to achieve an absorption of µ*Q of about 1 at the edge.

The γ- Fe2O3 and also the three α-Fe2O3/Fe3O4 mixtures were prepared as Pellet. Here the sample material was mixed with Hoechst Wax C in a ratio of 1:6, mixed in a vortex shaker and then pressed with a hydraulic press with a Pellet diameter of 13 mm. The amount of the wax/sample powder material was weight before inserting in the press to the amount of Q to achieve a µ*Q of about 1 with a 13 mm Pellet.

Shifts of the energy axis as well as a widening or compression of this axis could be present when comparing the data with other data sets of other spectrometer or synchrotron radiation facilities, since no precise energy calibration was carried out due to the reason that the samples were compared to the measured references and would have the same shift, widening or compression.

 

XRD: Two different commercial XRD set ups have been used. For the Mexican magnetite the Benchtop XRD spectrometer Bruker D2Phaser with a Cobalt X-ray source and a SSD160 detector (active length = 12 mm) was used. The measurement range was 10°- 90° 2theta with 0.014° step size and 4.8 s/step, resulting in a total measurement time of 8h. During the measurement the sample was rotated with 10 rpm. The sample was filled in PMMA-holders (Ø 2.5 mm) using the top-loading technique. The analysis was carried out using a 1-mm fixed divergence slit, a 2.5° primary and a 4° secondary soller collimator, a fixed knife edge (3 mm above the sample surface), and an Fe Kβ filter (2.5).

For the X-ray diffraction measurements of the α-Fe2O3/Fe3O4 mixtures and the pure references a Panalytical X’Pert PRO diffractometer with a Bragg-Brentano setup was used. The diffractometer operates with a Cu anode and without a monochromator (Cu-Kalpha radiation) at 40 kV and 30 mA. The diffraction data were obtained over a measurement range of 10–120° 2theta. Samples were applied flat on a cut-off Si wafer attached to the sample holder.

 

Mössbauer: Mössbauer spectroscopy was performed at a MIMOS II type spectrometer with a 57Co source (in rhodium matrix). For the analyses the 57Fe-γ-line E = 14.4 keV was used and α-iron (α-Fe foil) was applied for the velocity calibration before the samples were analyzed. The samples were prepared in plastic powder sample holders and measured in transmission mode at room temperature. The measurement time varied between 12 h and 120 h depending on the sample.

 

Information on data sets

XAFS - this folder contains the XAFS spectra as intensity file with I0 (without the sample) and the It (transmission signal through the sample) for each sample. Multiple samples (It) share the same I0 and are therefore in the same data set. The Number in the filename between “XAFS“ and “data-set..” is the date of the measurement in the following format: YYYY_MM_DD. The first column in each file is the energy in unit eV. The abbreviation “WP” after each sample name in the header means “Wax Pellet” and indicates that the measurement was performed on a sample prepared as a wax pellet, the number (WP1) indicates the number of the pellet. Two pellets of each mixture were prepared to investigate the influence of the sample preparation. If the sample name is missing “WP#” the sample was prepared on adhesive tape as described above. The information on the contents of each data set as well as the measurement time (t = #h) for each It of the sample/reference can be found in data_dictionary_v2.txt.

The intensity is normalized to counts per 1800 seconds in a 0.25 eV (for data-set-1) and 1 eV (for data-set-2, data-set-3 and data-set-4) energy interval with the indicated central bin energy.

 

XRD - this folder contains the raw intensity files over 2theta (ASC-file). Each sample has its own file with the first column for the 2theta in unit degree and the second column for the measured intensity.

The Number in the file name between XRD and sample name (e. g. Fe2O3, 30-70) is the date of the measurement in the following format: YYYY_MM_DD.

 

MOESSBAUER - this folder contains the recoil Lorentz site analysis fit data of the samples. The files  consist of the observed intensity (Iobs) over the velocity (v (mm/s)), including the calcucalted intensity (Icalc) and the fits of the subspectra (Sextet Site 1, etc. ).  Each sample has it owns file. While the references substances Fe2O3 and Fe3O4 were measured between 2016 and 2019, the MexicanMagnetite was measured 2020. An exact measurement date can’t be determined anymore.

 

The corresponding sample to the short cut name (e. g. Fe2O3, 30-70,..) in the files can be found above and is listed in the data_dictionary.txt file as well.