CopyrightJCPDS - International Centre for Diffraction Data 2003, Advances in X-ray Analysis, Volume 46.

ANALYSIS OF GEOLOGIC MATERIALS USING RIETVELD

QUANTIATIVE X-RAY DIFFRACTION
Robin M. Gonzalez, Thomas E. Edwards, Timothy D. Lorbiecke, Ryan S. Winburn, and
John R. Webster*
Division of Science, Minot State University, 500 University Ave. W. Minot, ND 58707
ABSTRACT
Rietveld quantitative X-ray diffraction (RQXRD) was used to quantify the mineralogy of a
volcanic rock (dacite). To assess the success of the RQXRD method, the bulk mineralogy of the
dacite was determined through a combination of optical study of phenocrysts (plagioclase,
augite, orthopyroxene, and Fe-Ti oxide) and detailed study of the groundmass using a scanning
electron microscope with an energy dispersive X-ray (SEM/EDX) analysis system. The
groundmass consisted of distinct crystals of feldspar, pyroxene, and Fe-Ti oxide, and patches of
very fine-grained mixtures (referred to as funkalite) of feldspar, SiO2 phase, and Fe-Ti oxide.
Groundmass volume percentages were determined by point counting high magnification SEM
photomicrographs. These data were combined with phenocryst percentages and converted to
weight percentages. The optical/SEM and RQXRD results compared rather well, suggesting
RQXRD can provide a relatively rapid method for quantifying the mineralogy of volcanic rocks.
INTRODUCTION
The Rietveld method has been determined to provide relatively accurate results when applied to
coal combustion by-products [1,2,3]. The Rietveld method has been applied to igneous rocks [4],
including volcanic rocks. Volcanic rocks in general have a porphyritic texture (having two
distinct crystal size populations) that reflects a two-stage cooling history. Slow cooling at depth
results in phenocrysts (larger crystals) and rapid cooling upon ascent and eruption results in
small crystals and/or glass that comprise the groundmass. Phenocrysts can be identified and
quantified by optical microscopy, but the groundmass is too fine-grained to be studied optically.
Use of a scanning electron microscope (SEM) to quantify the mineralogy, while suitable, is not
feasible for routine work because of the time involved.
Rietveld quantitative X-ray diffraction (RQXRD) is well suited for quantifying the mineralogy of
volcanic rocks. However, evaluating the success of the Rietveld method for volcanic rocks is
difficult because the groundmass (typically the majority of the rock) is too fine-grained to study
by optical microscopy. RQXRD data have only been compared previously with normative
mineralogy [4]. To obtain the "observed" bulk mineralogy needed to assess the RQXRD method,
the groundmass mineralogy must be quantified and combined with phenocryst abundances
determined by optical microscopy. A major focus of this study was to characterize the
groundmass of a volcanic sample using a SEM with an energy dispersive X-ray (EDX) analysis
system.
This study involved testing RQXRD using a dacite sample (TL-11) from the central Oregon
High Cascades. This sample exhibited clear distinction between phenocrysts and groundmass.
The phenocrysts were previously quantified using optical microscopy (point counting). They
consisted of plagioclase feldspar, less abundant augite, orthopyroxene, and Fe-Ti oxide, and a
trace amount of olivine. Numerous phenocrysts were analyzed using an electron microprobe.
SEM/EDX METHOD
The SEM (JEOL SM-35CF) was used to obtain digital backscatter electron (BSE)
photomicrographs at high magnifications (4000X). BSE images (Figure 1) are best for
distinguishing phases because intensity varies with the average atomic weight of the materials.
These photomicrographs were used as a guide during EDX microanalysis. Microanalysis was
carried out in both spot mode (electron beam stationary) and in area mode (scanning at high

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CopyrightJCPDS - International Centre for Diffraction Data 2003, Advances in X-ray Analysis, Volume 46.

magnification). Five sites in the groundmass of TL-11 were studied to obtain representative
analyses of the groundmass components.
Once they were identified using EDX microanalysis, the volume percentages of the minerals in
the 4000X BSE photomicrographs were determined. This was done by drawing the borders of
the minerals using a computer drawing program (Figure 2). A grid was superimposed on each
"digitized" image and was used to point count the volume percentage of each constituent of the
groundmass. The constituents consisted of distinct crystals of feldspars, pyroxenes, and Fe-Ti
oxides, and patches of very fine-grained mixed phases informally referred to here as "funkalite".

B
plagioclase
feldspar
phenocrysts

Fe-Ti oxide
groundmass

funkalite

Area of B

alkali
feldspar

Fe-Ti oxide

augite phenocrysts

Figure 1. SEM backscatter electron photomicrographs of TL-11. (A) View showing basic nature of the
sample. (B) Enlarged view of the groundmass. Patches of funkalite, a mottled mixture of alkali feldspar,
SiO2-phase, and minor Fe-Ti oxide, are found between microcrysts of alkali feldspar and Fe-Ti oxide.

Figure 2. SEM backscatter electron photomicrographs of TL-11. (A) Site 2. (B) Site 2 digitized. (C) Site
4. (D) Site 4 digitized. Yellow: feldspar; red: Fe-Ti oxide; blue: pyroxene; white: funkalite; green: voids.

Because the funkalite consisted of a mixture, its volume percentage had to be distributed among
its component phases. This was done using recalculations of EDX analyses of funkalite. A
feldspar recalculation spreadsheet was used to determine weight percentages of feldspar, SiO2
phase, and Fe-Ti oxide. Fe- and Ti-oxide were assigned to Fe-Ti oxide. Then the SiO2 in the
analysis was manually adjusted (reduced) until the remaining SiO2 (and other oxides) yielded
good feldspar stoichiometry. The weight percentage of the subtracted SiO2 was assigned to the
SiO2 phase, and the remaining (appropriate) oxides to the feldspar component of the funkalite.
The weight percentages of the funkalite components were converted to volume percentages using
appropriate densities. The volume percentages were then combined with volume percentages of
the discrete groundmass minerals. These total groundmass percentages were then combined with

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the phenocryst percentages to obtain the bulk sample volume percentages. Finally, all volume
percentages were converted to weight percentages using appropriate densities.
OPTICAL AND SEM/EDX RESULTS
The abundances of phenocrysts and groundmass quantified through previous optical point
counting (500 points) are presented in Table 1. Figure 3 is a typical thin section view showing
the four minerals that were quantified: plagioclase, augite, orthopyroxene, and Fe-Ti oxide.
Olivine is also present in trace amounts, but was not encountered during the point counting.
Table 1. Volume percentages from optical point counting
Phenocrysts

Plagioclase
Olivine
Augite
Orthopyroxene
Fe-Ti Oxide

Groundmass

Volume %
21.6
Trace
1.4
0.4
0.8
75.8

Orthopyroxene
Plagioclase Feldspar

Augite
Fe-Ti oxide
Augite

Figure 3. Plain-light photomicrograph of TL-11 showing representative

phenocrysts and abundant groundmass. The area shown is 2 mm wide.

High magnification BSE images showed that the groundmass consisted of crystals and patches of
funkalite. The boundaries between them varied from sharp to irregular and almost gradational.
Figure 2 illustrates the variability in the appearance of the funkalite. It varied from light swirly
heterogeneous patches (e.g., Figure 2A) to dark homogeneous patches (e.g., Figure 2C). The
heterogeneous funkalite typically appeared to be composed of feldspar, a SiO2 phase, and trace
amounts of Fe-Ti oxide.
Electron microprobe analyses of phenocrysts, spot EDX analyses of groundmass crystals, and
area EDX analyses of funkalite show that mineral compositions vary among phenocryst and
groundmass crystals. Feldspar and pyroxene compositions are plotted in Figure 4. Plagioclase
feldspar phenocrysts varied from An33 to An67 (Figure 4A). Groundmass feldspar crystals were
dominantly Na-rich (albite-rich), while the feldspar component of funkalite was alkali feldspar
that was generally more K-rich. Augite phenocrysts had a rather limited compositional range,
while orthopyroxene had a wider range (Figure 4B). Groundmass pyroxene crystals consisted of
augite that is more Fe-rich and less calcic than augite phenocrysts, and pigeonite. Fe-Ti oxides
were dominantly magnetite-ulvospinel solid solutions (Mt47Usp53 to Mt56Usp44), but there was

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207

some hematite-ilmenite solid solution (Hm08Ilm92). Groundmass Fe-Ti oxide compositions

(Mt63Usp37 and Hm15Ilm85) were slightly different than phenocryst compositions.
CaAl2Si2O8

Wollastonite
Ca2Si2O6

Anorthite

Pla
gio
cla
se

Fe
lds
p

ar

Bytownite

Labradorite

Diopside
CaMgSi2O6

Hedenbergite
CaFeSi2O6

Andesine
Augite

Oligoclase
Albite
NaAlSi3O8

Alkali Feldspar

Mg2Si2O6
Enstatite

KAlSi3O8
Orthoclase

Orthopyroxene

Pigeonite

Fe2Si2O6
Ferrosilite

Figure 4. Plots of phenocryst and groundmass mineral compositions. (A) An-Ab-Or ternary showing the
compositions of feldspar phenocrysts (red), groundmass crystals (yellow), and the feldspar component in
the heterogeneous funkalite patches (green). The purple shaded field shows feldspar components based
on analysis of dark patches. (B) Wo-En-Fs ternary for pyroxene phenocrysts (red) and groundmass
crystals (yellow).

Area EDX analyses carried out on the two types of funkalite showed significant differences in
the abundances of feldspar, SiO2 phase, and Fe-Ti. The dark patches contained more SiO2 phase
(52-97 wt.%) compared to the normal heterogeneous funkalite (8-53 wt.%), which contained
more feldspar component. The compositional ranges of the feldspar components of the two types
of funkalite are quite similar, except for the somewhat more limited range and slightly lower Ca
contents exhibited by the dark homogeneous funkalite patches.
Volume percentages determined from point counting of the digitized images of each groundmass
site are presented in Table 2. The funkalite components were determined by recalculation of an
average EDX chemical analysis for each of the five groundmass sites. The groundmass volume
percentages were normalized to the percentage of groundmass in the bulk sample and then
combined with phenocryst percentages. The combined bulk mineralogy is presented in Table 3.
The calculated weight percentages comprise the known values with which the RQXRD results
are compared.
Table 2. Groundmass mineralogy (vol. %)
Site 1
Feldspar

Site 2

Site 3

Site 4

Site 8

Average

49.706

41.103

29.081

82.060

43.922

49.174

31.272

40.142

52.795

1.245

34.727

32.036

Orthopyroxene

0.882

1.912

3.407

4.810

1.939

2.590

Fe-Ti Oxide

3.676

0.735

1.743

1.100

2.013

1.853

0.646

0.440

0.733

0.000

0.255

0.355

14.117

15.668

12.242

10.775

17.143

13.989

SiO2 Phase

G = distinct groundmass crystals, F = funkalite

CopyrightJCPDS - International Centre for Diffraction Data 2003, Advances in X-ray Analysis, Volume 46.

Table 3. Bulk Mineralogy of TL-11

Feldspars

Pyroxenes

Plagioclase
Na-rich
Alkali
Augite
Orthopyroxene
Pigeonite + Augite

Fe-Ti Oxides

SiO2 Phase

Volume
%
21.600
37.274
24.283
1.400
0.400
1.963
0.800
1.405
0.269
10.604

P
G
F
P
P
G
P
G
F
F

Density
3
(g/cm )
2.68
2.62
2.62
3.26
3.57
3.57
5.20
5.12
2.12
2.65

Weight % of
Bulk Sample
21.20
35.77
23.31
1.67
0.52
2.57
1.52
2.63
0.50
10.29

Weight % by
Mineral Type
80.28

4.76

4.65

10.29

P = phenocrysts, G = distinct groundmass crystals, F = funkalite

RIETVELD METHODS AND RESULTS

The XRD data was collected using a Philips XPert MPD with 1 fixed divergence and antiscatter slits and a 0.2 mm receiving slit. The data was collected from 20-80 2 counting for 2
seconds per step. The data were analyzed using the software program General Structure
Analysis System (GSAS) [5] using a previously described refinement protocol [1-3].
Multiple refinements were performed due to the large number of phases believed to be present
within the sample as outlined previously [2, 3]. Weight percentages for ten different minerals
were determined with an eleventh phase (rutile) being the internal standard. Due to limitations in
the analysis software, only nine phases could be analyzed at a time. Five individual refinements
were completed so that a representative average could be taken. Through analysis of the final
refinement plots it was observed that a few smaller peaks were left unaccounted for. Since all
phases are not accounted for in each refinement, every plot will have peaks that remain
unaccounted for. Only those peaks that remained after all refinements were completed can be
representative of an additional phase.
The results of five refinements are given in Table 4, along with the average weight percentages
for each phase. Although the weight percents vary among the refinements, the relative amounts
are consistent.
Table 4. Weight percent data from five separate refinements

Feldspars

Anorthite
Albite
Sanidine
Microcline
Pyroxene
Augite
Fe-Ti Oxides Ulvospinel
Magnetite
Illmenite
Hematite
SiO2 Phase
Cristobalite
Amorphous/Unaccounted*

Average

6.72
40.57
28.60
10.40
3.79

7.58
39.18
30.54
11.53

5.85
42.95
18.07
5.92

4.97
38.63
28.16
11.55
4.21
1.00

5.98
46.50
21.15

6.22
41.57
25.30
9.85
4.00
1.44
0.56
0.86
0.87
9.23

1.19

1.63
0.35

0.94
10.03
-2.23

0.69
10.07
-1.56

0.40
1.53
0.98
6.75
17.54

0.85
9.51
1.12

1.70
0.30
0.21
0.85
9.77
13.54

* calculated by subtracting crystalline phase percentages from 100%

Totals by
Mineral Type
82.94

4.00
3.73

9.23
0.10

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CopyrightJCPDS - International Centre for Diffraction Data 2003, Advances in X-ray Analysis, Volume 46.

DISCUSSION
Refinement number 3 (Table 4) seems to deviate the most from its counterparts. This deviation
is most apparent in the low values for the phases sanidine, microcline, anorthite and cristobalite.
Variability among the refinements is due to peak overlaps and the choice of phases within each
refinement. There is also some uncertainty in the optical/SEM data. Additional optical point
counting and detailed study of groundmass sites might improve the results. Also, it is unclear at
this time whether the dark type funkalite patches are completely crystalline. Their homogeneous
nature suggests they could be patches of SiO2 phase, with other oxides in EDX analyses coming
from surrounding materials, rather than a mixed-phase material. Despite uncertainties, the
RQXRD results compare quite well with optical/SEM results. Table 5 summarizes the bulk
mineralogy as determined by the two methods. These results suggest that it is feasible to
quantify the mineralogy of volcanic rocks using RQXRD.
Table 5. Comparison of optical-SEM and RQXRD results
Feldspars
Pyroxenes
Fe-Ti Oxides
SiO2 Phase
Amorphous/Unaccounted

Optical-SEM
80.3
4.8
4.7
10.3

RQXRD
82.9
4.0
3.7
9.2
0.1

Future optical/SEM work on TL-11 will involve additional optical point-counting and detailed
study of additional groundmass sites, with attention to the nature of the dark homogeneous
funkalite patches. Future RQXRD work may involve determining the additional phase(s) that
presently appears to be missing in the refinements. Modifying structures and site occupancies
used in the refinements might also improve results. In addition, refinement of the compositions
of solid solution phases will be investigated. Initial studies will focus on the feldspar minerals,
followed by investigation of the iron-containing phases.
If RQXRD can routinely be used to successfully quantify the mineralogy of volcanic rocks and
the compositions of solid solution phases, it will provide a powerful tool in the study of volcanic
rocks. While this use of RQXRD will not replace detailed microanalysis of minerals in igneous
rocks, it could provide a rapid screening tool for selection of samples that are best suited for
detailed microanalysis. Future work will involve additional volcanic rocks, including samples
that contain glass in the groundmass and samples that have different phenocryst compositional
ranges. Of particular interest is plagioclase and whether RQXRD could be used to distinguish
samples that have a limited plagioclase phenocryst compositional range (i.e., non-mixed) from
those that have a wide and/or bimodal range (i.e., mixed).
ACKNOWLEDGEMENTS
A Minot State University Small Grant provided partial funding for this research. The Materials
Characterization Lab at North Dakota State University provided the XRD scan.
REFERENCES
[1]
[2]
[3]
[4]
[5]

Winburn, R.S., Lerach, S.L., Jarabek, B.R., Wisdom, M.A., Grier, D.G., and McCarthy,
G.J. (2000). Adv. X-Ray Anal., 42 , 387-391.
Winburn, R.S. (1999). Ph.D. Dissertation, North Dakota State University
Winburn, R.S., Grier, D.G., Peterson, R.B., McCarthy, G.J., and Grier, D.G. (2000). Powd.
Diff., 15, 163-172.
Hill R.J., Tsambourakis, G., and Madsen, I.C. (1993). J. Pet., 34, 867-900.
Larson, A.C., and Von Dreele, R.B. (1994). Los Alamos National Laboratory Report
LAUR 86-784.

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