The Rigaku Journal

Vol. 16/ number 1/ 1999

CONTRIBUTED PAPERS

ANALYSIS OF LIMESTONES AND DOLOMITES

BY X-RAY FLUORESCENCE*

BRADNER D. WHEELER, PHD.

Rigaku/USA, 199 Rosewood Drive, Danvers, MA 01923, USA

Sources of calcium are generally widespread and quite extensive. These sources are of limestone, dolomite, marl,
chalk, and oyster shell. Cement plants account for nearly half the demand while more than two hundred lime plants in the
United States and Puerto Rico consume about twenty five percent. Since the chemical composition of the limestone or
other sources of calcium is critical in the cement and the lime industry, particularly for the deleterious compounds such as
Na2O, MgO, P2O5, and K2O, accurate determinations are critical. Due to the tonnage per hour, these determinations must
be made rapidly and accurately. X-ray fluorescence can thereby satisfy this need for accuracy and precision.
Production of lime is performed by calcining limestone and the industry is generally located and concentrated in the
States of Michigan, Pennsylvania, and Missouri. The resulting product is quicklime-CaO, or hydrated lime-Ca(OH)2.
Substantial amounts of quicklime is further processed into calcium carbide in order to produce acetylene gas. In this case,
the determination of P2O5 is critical since minor amounts of phosphorous in the acetylene gas can cause premature
explosions. Other uses for lime are well known in the treatment of water, the paper and pulp industry, and the steel
industry for the production of slag to remove impurities. Dolomitic lime is heavily utilized in the manufacture of
magnesite refractories by reacting the dolomitic lime with brines from the Michigan basin to produce MgO and CaCl2.
Sample preparation for these materials has been performed by grinding and pelletizing or fusion with Li2B4O7. In
addition to the chemistry, matrix and interelement effects will be discussed as related to the chemical analysis by X-ray
fluorescence.

Introduction fluence the intensities of the analytical lines.

Calcium carbonate and calcium-magnesium
carbonate in the form of limestone, dolomite, marl,
chalk, and Oyster shell are one of the most widely
utilized non-metallic materials in the industrial world.
The largest use of limestone or calcium carbonate is in
the cement industry where it is used as a source of
CaO and also in the concrete industry where it is used
as the primary coarse aggregate. Following the
cement industry, the second largest user would be the
lime industry.
Geological materials present numerous problems
as a result of the preponderance of low atomic
numbered elements in a variable mineralogical and
elemental matrix. X-ray fluorescence can provide the
analyst with an accurate and precise method providing
the analytical techniques are properly addressed and
are consistent from sample to sample. The most ser-
ious problems to solve are absorption and enhance-
ment effects, mineralogical differences among
samples, and particle size effects which often in-
* Presented at the ASTM Committee on Lime, C-7, December 8,
Nashville, Tennessee.
Consequently, relative intensities of a standard and an
unknown sample are often only approximate mea-
surements and not directly proportional to the
concentration since the matrix, in addition to the
concentration of the assayed element as related to the
measured characteristic radiation must be corrected
for enhancement, absorption, and possible peak
overlaps. These matrix effects are generally
considered as absorption, enhancement, peak over-
laps, mineralogical differences, and inhomogenity of
the sample particles. Consideration of these problems,
thereby providing a useful and workable procedure by
X-ray fluorescence, has been approached by the use
of internal standards [1], comparison to standards
approximate in composition to the unknowns [2],
fusion and dilution with transparent materials such a
lithium-tetra-borate [3-5], reduction of particle sized
by fine grinding [6-9], and mathematical corrections
[10-14]. The method utilized by the author employs
the powder method, fine grinding and pelletizing, and
empirical calculations for corrections due to ab-
sorption, enhancement, and peak overlaps.

16 The Rigaku Journal

 Analysis of any material by X-ray fluorescence is
best applied to materials where the compositional
range is reasonably small. Calcium/calcium-mag-
nesium carbonate rocks fall into this category even
though the calcium/ magnesium ratios plus the
argillaceous fractions are quite variable. In order to
successfully apply an X-ray fluorescence technique,
the characteristics affect the reproducibility and
accuracy must be identified and corrected. These
variables which can cause errors in the analysis are
deviations in the particle size, mineralogy, and
interelement effects due to varying chemical
composition among samples.
Particle Size
Reproducible and accurate results by the powder
method in the quantitative analysis of mineralogical
samples requires proper sample preparation in order to
minimize intensity fluctuations as a function of
variations in the particle size and distribution. Burn- Fig. 1 Grinding time versus intensity.
stein [16] has illustrated that the fluorescent intensity
from a pure material will increase as the particle size is
decreased. In limestone and dolomites the intensities
from several elements may all increase, decrease, or
one may decrease while others increase. Campbell
and Thatcher [17], measuring calcium in Wolframite
where the calcium may be present as a carbonate,
tungstate, or phosphate supported Burnstein's work.
Differences in intensities were observed for equal
concentrations of calcium in three chemical states
when the particle size is large as compared to the
effective depth of penetration of incident X-ray.
Extensive grinding illustrated the intensities from the
various mineralogical forms approach a common
value by reducing the absorption within the individual
particles to a small value (-325 mesh). Figure 1
illustrates the relation of intensity with grinding time
or a reduction in particle for Ca-Mg carbonate rocks.
Reduction in particle size causes a reduction in the
intensities of iron, sulfur, and potassium while the
intensities of calcium and silica are increased. As the Fig. 2 Pelletizing pressure versus intensity.
size of the individual particles is reduced, the
intensities stabilize. Further reduction in particle size
through continued grinding does not promote any Examination of Figure 2 reveals that in order to
additional improvement in the intensities, Referring to reproduce a consistent pellet, a pelletizing pressure of
the example on Figure 1, the minimum grinding time fifteen tons per square inch should be used.
would be five minutes. A lesser amount of time could lnterelement Effects
cause significant intensity/concentration deviations
Quantitative analysis by X-ray fluorescence of
among the standards and samples. Now that a grinding
any material requires that the measured intensity of a
time has been established, determining the proper
particular element is proportional to the percent com-
pelletizing pressure must be determined. A similar
position. A matrix such as a limestone or a dolomite
study was performed as illustrated on Figure 2.

Vol. 16 No. 1 1999 17

may reveal that the intensity of an element may not be
directly proportional to the concentration due to result
of an additional element within the sample. This non-
linearity is frequently referred to as the interelement
effect and may also be referred to as enhancement or
absorption. When the characteristic radiation of one
element excites another element, enhancement oc-
curs. Absorption is observed when one element in the
sample matrix has an absorption edge on the low
energy side of the element of interest or has a mass
absorption coefficient larger than the element of
interest at the energy level of that element. Examples
of these effects are illustrated on Figure 3 (Mass
Absorption Coefficient vs Energy in KEV). Since the
Si Kα line occurs just on the high energy side of the
Al K-edge, secondary fluorescence will take place
and conversely, silica is strongly absorbed by
aluminum. A similar case is observed in the po-
tassium-calcium System where calcium is strongly
absorbed by potassium since the Ca Kα line lies just
on the high energy side of the K K-edge as illustrated
on Figure 3. An additional complication is the fact that
iron has a high mass absorption coefficient at the
energy levels of the lower Z elements, thereby acting
as a strong absorber.
Although absorption and enhancement effects
can be severe, mathematical corrections can easily be
applied. Numerous methods have been proposed [10-
14]. The author has proposed a method described by
LaChance [11] where a relationship is established that
the relative intensity of a characteristic line in a binary
system is directly proportional to the weight fraction
of a given element (A) plus (B) however must sum to
unity. The expression would be as follows;
RA = (Ca ) ( 1+ Cb αAB ) (1)
Fig. 3 Elemental absorption curve.
18
RB = ( Cb ) (1+ Ca αBA) (2)
Defining αAB and αBA
( µ csc θ + µ csc θ ) ⋅ (B − 1)
αAB =
1 1 2 2
(3)
( µ csc θ + µ csc θ ) ⋅ A
1 1 2 2
( µ csc θ + µ csc θ ) ⋅ ( A − 1)
1 1 2 2
αBA = (4)
( µ csc θ + µ csc θ ) ⋅ B
1 1 2 2
where
(µ1)A and (µ1)B= the mass absorption coefficients of elements A
and B at the effective wavelength for the
excitation of the A radiation
(µ2)A and (µ2)B=the mass absorption coefficients of elements A
and B at the effective wavelength for the
excitation of the B radiation
θ1 and θ2 = the angle of incidence of the primary X-ray beam and
the take off angle of the secondary radiation
Ca and Cb =the weight fractions of elements A and B
Ra and Rb = the relative intensities of elements A and B expressed
as ratios of net intensities of the elements A and
B in the sample to the net intensities for the pure
elements A and B
Calibration of the standards involves an iterative
process according to Equations 3 and 4 which estab-
lishes the a coefficients which are then assigned to
Equations 1 and 2. The unknown sample data is then
processed through multiple regression analysis
utilizing Equations 1 and 2.
Sample Preparation
As previously discussed, particle size and
distribution can have an effect on the intensities of
most elements with the most severe being at the low Z
end of the periodic table. An illustration of this fact,
Figure 1, displays the effect of grinding time trans-
lated into smaller sized particles with increased
grinding time. Eight (8) separate samples of single
standard of five (5) grams and 0.1 grams of Na-
stearate as a grinding aid were placed in a tungsten
carbide rotary swing mill and ground for one (1) to
eight (8) minutes. The resulting powder was then
pelletized under 15 tons per square inch with boric
acid as a backing material. Each pellet was analyzed
with the resulting intensities plotted as a function of
grinding time (Figure 1). The grinding curve indi-
cated a minimum grinding time plus one (1) minute
for a total of six (6) minutes.
The Rigaku Journal
 Table 1. Instrumental Operating Conditions for Limestones and Dolomites.

Element Na2O MgO Al2O3 SiO2 P2O5 SO3 K2O CaO TiO2 MnO Fe2O3 SrO

ANODE Rh

ANODE VOLTAGE, KV 30 50

ANODE CURRENT, MA 130 80

SLIT Coarse

CRYSTAL RX-40 PET Ge LiF

DETECTOR FP-C SC

FILTER None

PEAK 2θ ANGLE 17.05 14.15 144.65 109.04 141.10 110.80 70.00 61.95 86.18 62.96 57.49 25.13

COUNTING TIME, S 40 20

PHA LOWER 50 100

PHA-UPPER 450 300

ATMOSPHERE Vacuum

Instrumentation that the CaO in the unknowns was initially

A Rigaku RIX 3100 X-ray spectrometer with a 4
kW generator was utilized for this analysis and was
operated under the instrumental operating parameters
as described on Table 1.
Results and Conclusions
The samples utilized in this study were seven (7)
standards supplied by the National Bureau of
Standards [18], Ash Grove Cement Company [19].
Hercules Cement Company [20], and well charac-
terized unknown samples from Medusa Cement
Company [21]. The standards and unknowns were
derived from diverse geographical and geological
areas. In addition the mineralogical structure varied
from calcite (rhomboidal-R-3c), vaterite (hexagonal-
P63mmc), aragonite (orthorhombic-Pnm), and ara-
gonite (orthorhombic-Pmca) as listed in appendix A.
The results of analysis is contained on Table 2,
while the individual calibration curves are contained
in appendix B. A typical spectra of limestone is con-
tained in appendix C. Calcium oxide and magnesium
oxide, the main components in Ca/Mg carbonate
rocks, exhibited absolute errors of approximately two
to four percent relative utilizing a simple least squares
regression analysis. Utilizing the theoretical alpha
routine as outlined by LaChance [11] with a multiple
least squared analysis, these errors were reduced to
0.07 and 0.05 percent respectively. It should be noted
determined by a KMnO4 titration with no attempt to
differentiate between CaO and SrO. In the KMnO4
titrimetric determination of CaO, both the CaO and
SrO are both precipitated as a calcium-strontium
oxalate and when titrated with KMnO4, the oxalate
ion is being determined. As a result, the determined
value by this method will be CaO plus SrO. In a
limestone or a dolomite, the SrO could be from 0.05
to 0.3 percent. Therefore, since X-ray fluorescence
determines CaO and SrO separately, the SrO and CaO
determination by X-ray fluorescence must be com-
bined in order to agree with the KMnO4 titrimetric
calculation.
Conclusions
The results of analysis illustrate that X-ray
fluorescence is a viable technique for the analysis of
limestone and dolomite. It further illustrates that, with
proper sample preparation, mineralogical differences
become insignificant. Data reduction the use of
theoretical alphas automatically solves the problems
associated with absorption and enhancement effect.
References
[1] Dwiggins, C. W. Jr., and Dunning, N. H., Quantitative
Determination of Traces of Vanadium, Iron, and Nickel
in Oils by X-ray Spectrography, Anal. Chem. 32, 1137-
1141, 1960.

Vol. 16 No. 1 1999 19

 [2] Brown, 0. E., “Use of X-ray Emission Spectroscopy in
Chemical Analysis of Cement, Raw Materials”, And Raw
Mix, ASTM Annual Meeting, 1963.
[3] Moore, C., “Suggested Method for Spectrochemical
Analysis of Portland Cement by Fusion with Lithium
Tetraborate Using an X-ray Spectrometer", ASTM
Report No. E-2, 5MlO-26.
[4] Harvy, P. K., Taylor, D. M., Hendry, R. D., and Bancroft,
F., “An Accurate Fusion Method for the Analysis of
Rocks and Chemically Related Materials by X-ray
Fluorescence”, X-ray Spectrometry, 2, 33-34, 1972.
[5] Claisse, F., “Accurate X-ray Fluorescence Analysis
Without Internal Standards", Norelco Rep. 4, 1957.
[6] Wheeler, B. D., “Cement Raw Mix Control through X-ray
Emission Spectroscopy”, Proc. Third Forum the geology
of Industrial Minerals, Spec. Dist. 34, University of
Kansas, 1967.
[7] Hooper, P. R., “Rapid Analysis of Rocks by X-ray
Fluorescence”, Analytical Chemistry, 36, 1964.
[8] Wheeler, B. D., “Accuracy in X-ray Spectrochemical
Analysis as Related to Sample Preparation”,
Spectroscopy, vol. 3, No. 3, pp 24-33, March, 1998.
[9] Kester, B., AIEE Cement Industry Conference,
Milwaukee, Wisconsin, 1960.
[10] Wheeler, B. D., and Newell, D., “Chemical Analysis of
Mg-Cr Refractories by X-ray Fluorescence, Fall Meeting
of the American Ceramic SOCIETY, Refractories
Division, Paper #13-RI-76F, October 9, 1972.
[11] LaChance, G. R., and Traill, R. J., “A Practical Solution
to the Matrix Problem in X-ray Analysis”, Canadian
Spectroscopy, vol. 11, nos. 2-3, March-May, 1966.
[12] Lucus-Tooth, H. J., and Price, B. J., “A Mathematical
Method for the Investigation of Interelement Effects in X-
ray Fluorescence Analysis”, Metallurgia, vol. LXIV, no.
383, Sept., 1961.
[13] Rasberry, S. D., and Heinrich, K. F. J., Calibration of
Interelement Effects in X-ray Fluorescence Analysis,
Analytical Chemistry, vol. 46, no. 1, Jan., 1974.
[14] Hasler, M. R., and Kemp, J. W., “Suggested Practices
for Spectrochemical Computations”, ASTM Committee
E-3, Report SM 2-3, American Society for Testing &
Materials, Philadelphia, PA, pp 72-82, 1957.
[15] Sherman, J., “The Correlation Between Fluorescent X-
ray Intensity and the Chemical Composition”, ASTM
Special Publication, no. 157, pp 27-33, 1954.
[16] Burnstein, F., Particle Size and Mineralogical Effects in
Mining Applications of X-ray Analysis, Denver Research
Institute, University of Denver, 1962.
[17] Campbell, W. J., and Thatcher, D., Advances in X-ray
Analysis, vol. 2, University of Denver, 1958.
[18] National Bureau of Standards, Washington, D.C.
[19] Ash Grove Cement Company, Kansas City,MO.
[20] Hercules Cement Company, Bethlehem, PA.
[21] Medusa Cement Company, Dixon, IL.

20 The Rigaku Journal

 Appendix A. Listing of Standards and Source

STD GEOLOGIC FORMATION REGION SOURCE

LS-1 Burlington Missouri Ash Grove Cement Co.

LS-2 Raytown Kansas Ash Grove Cement Co.

LS-3 Squamish British Columbia Ash Grove Cement Co.

LS-4 Kimswick Missouri Ash Grove Cement Co.

LS-5 Jacksonburg Pennsylvania NBC

LS-6 Jacksonburg Pennsylvania Hercules Cement Co.

LS-7 Farley Nebraska Ash Grove Cement Co.

Appendix B. Typical Limestone Spectra

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