Energy-dispersive X-ray fluorescence (EDXRF)

Poster T109 as a comprehensive method for mineral analysis of feeds

2018 ADSA
R. Ward1*, D. Ye1, A. Buman2, D. Pecard2 and D. R. Mertens3
1Cumberland Valley Analytical Services, Waynesboro, PA, 2Bruker AXS Inc., Madison, WI and 3Mertens Innovation & Research LLC, Belleville, WI

Introduction Materials and Methods Results and Discussion Results and Discussion
Energy Dispersive X-ray Fluorescence (EDXRF) is a method for • Sample preparation Calibration for P Zinc is an example of a trace mineral with a calibration that was
using X-ray Fluorescence to detect and measure elements •The standards and unknown samples were prepared and ran Number of standards 57 about average for these minerals
(minerals) in materials. EDXRF spectrometers use a primary as a loose powder Concentration range 0.15 to 0.60% of DM Calibration for Zn
radiation of X-Ray tube to excite all the minerals in a test sample and Energy lines settings Fixed 2.016 keV Number of standards 60
a detector collects the subsequent secondary fluorescence radiation •5.0 g of material was weighed out and placed into the 40-mm
diameter Chemplex Cup (PN 2144) Intensity model Net intensity Concentration range 13.4 to 134 ppm in DM
emitted from the sample.
Overlapping peaks None Energy lines settings Fixed 8.632 keV
•Sample in cup was supported with a 3.0µm Prolene Chemplex
Matrix correction Variable alphas Intensity model Net intensity
Sample Film (PN 3018A) selected for the best transmittance of
Coefficients Overlapping peaks None
light elements radiation
Matrix correction Variable alphas
Calibration
Offset (intercept) 0.03%
slope 0.00117 % / (cps/mA) Coefficients
R2 .959 Offset (intercept) 1.73 ppm
• Calibration samples included 20 TMR, 10 corn grain, 10 corn slope 9.252 ppm / (cps/mA)
Standard deviation 0.02%
silages, 12 legume and 8 grass forages
R2 .986
• Mineral analyses:
• Ca, P, Mg, K, Na, Fe, Mn, Zn, and Cu were determined by ICP Standard deviation 3.47 ppm
• S by combustion analysis
• Cl by titration

The intensity of the emitted fluorescence, in counts per second
(cps), is plotted versus the energy level, in keV, Each element or
mineral has peaks a specific energies and the location of the energy
peak identifies the mineral. The intensity of the peak is a function of
the concentration of the mineral. Because peaks of different
minerals can overlap, software is used to identify the peak that is
specific for detecting each mineral.
EDXRF spectroscopy is simple, involves minimum moving parts and
can detect minerals in a native sample that does not require ashing
the sample or extraction of minerals in strong acids. Typically, the
sample is ground and pressed into a hard pellet before EDXRF
analysis.
Results and Discussion
Calibration statistics were excellent for macro-minerals with R2 Figure 2. Spectral scan for P peak KA1 (3.696 keV) used for calibration.
varying from 0.941 (Mg) to 0.994 (K). Standard deviation of
calibration regressions varied from ± 0.02 to 0.07% of DM.
*************
Statistics of calibration were similar for trace minerals.
Sodium was an example of a mineral with the lowest calibration statistics,
yet its calibration was accurate. Perhaps calibration statistics reflects the
Detailed description of statistics and the energy peaks selected variability in chemical analysis for Na, and the low intensity and variability
for calibration are provided for some minerals to demonstrate the in the baseline and peak selected for calibration.
potential of EDXRF for determining mineral concentrations in
feeds. Calibration for Na
Calibration for Ca
Number of standards 60
Number of standards 58
Concentration range 0.01 to 0.72% of DM Figure 2. Spectral scan for Zn peak KA1 (3.696 keV) used for calibration.

Objective
Concentration range 0.01 to 2.65% of DM
Energy lines settings Fixed 1.047 keV
Energy lines settings Fixed 3.696 keV

• The objective of this study was to determine the speed and

Intensity model Net intensity
Intensity model
Overlapping peaks
Net intensity
Zn (peaks LB1 & LA1)
Summary
Overlapping peaks K (peak KB1)
accuracy of EDXRF spectroscopy when used on samples that Matrix correction Variable alphas Element n Range (in DM) R2 SD Peak (keV) Precision
Matrix correction Variable alphas
were dried and ground for routine chemical analysis in Coefficients Ca 58 0.01 to 2.65 % 0.986 ±0.07 % 3.696 ±0.01 %
commercial feed testing laboratories Coefficients P 57 0.15 to 0.60 % 0.959 ±0.02 % 2.016 ±0.00 %
Offset (intercept) -0.08%
Offset (intercept) 0.02% Mg 60 0.09 to 0.53 % 0.941 ±0.03 % 1.251 ±0.01 %
slope 0.00745 % / (cps/mA)
Materials and Methods slope 0.01142 % / (cps/mA) S 53 0.10 to 0.48 % 0.974 ±0.02 % 2.311 ±0.00 %
R2 .942 K 54 0.35 to 3.91 % 0.994 ±0.07 % 3.302 ±0.00 %
R2 .986 Cl 51 0.00 to 1.88 % 0.993 ±0.026 % 2.635 ±0.00 %
Standard deviation 0.05%
Standard deviation 0.07% Na 60 0.01 to 0.72 % 0.942 ±0.05 % 1.047 ±0.01 %
• Instrument BRUKER S2 PUMA XY Autochanger, Light Fe 57 20.8 to 1821 ppm 0.994 ±26.0 ppm 6.400 ±3.50 ppm
Elements (LE) Mn 58 4.61 to 138.3 ppm 0.963 ±7.11 ppm 5.895 ±1.04 ppm
Zn 60 13.4 to 133.5 ppm 0.986 ±3.47 ppm 8.632 ±1.71 ppm
• X-ray Source Target Material: Ag (Silver) Cu 59 1.23 to 24.9 ppm 0.956 ±1.35 ppm 8.044 ±0.44 ppm
• Mask: No Mask (34mm)
For the analysis of unknown samples the measurement time
• Measurement Mode Assisted Helium was 5 min without significant change in analytical precision.
• Detector X-Flash Silicon Drift Detector (SDD), Light This would allow to analyze 10-12 samples per hour , which can
Elements (LE) be a limitation for laboratories receiving 100s of samples per
day. In that case a second instrument can be used.
• Sample rotation: 0.5 rev/sec
• X-ray tube current is automatically adjusted based on
the count rate of 150,000 cps
Conclusion
• BRUKER SPECTRA.ELEMENTS software used for
calibration These initial results indicate that using EDXRF with
• Elements Na, Mg, P, S, and Cl were measured with 20 kV routine feed sample preparation offers an excellent
and no filter alternative to chemical analysis for the simultaneous
• Elements K, Ca, Mn, Fe, Cu, and Zn were measured with analysis of macro and trace minerals in feeds and feed
40 kV and a 500 µm Al filter mixtures.
Figure 1. Spectral scan for Ca peak KA1 (3.696 keV) used for calibration. Figure 3. Spectral scan for Na peak KA1 (1.047 keV) used for calibration.
• Measurement time for calibration samples was 9 min X-rays typically affect electrons in the inner most K and L shells of atoms.
per sample

ADSA-ASAS 2011 Joint Annual Meeting