NOTES" 23q

CALCITE STAINING: SEMIQUANTITATIVE DETERMINATION

OF F E R R O U S
IRON 1

R. C. L I N D H O L M
Department of Geology, The George Washington University, Washington, D.C. 20006
AND

R B. F I N K E L M A N
U. S. Geological Survey, Washington, D.C. 20242

ABSTRACT
Calcite phases with different amounts of ferrous iron (determined by microprobe analysis) are distin-
guishable by stud3' of stained thin sections and stained acetate peels. We have defined four such phases, they
are (a) non-ferroan calcite (0.0% FeO; red stain), (h) ferroan calcite I (0.5% to 1.5% FeO; red-purple
stain), (c) ferroan calcite II (1.5% to 2.5% FeO; purple stain), and (d) ferroan calcite I l l (2.5% to 3.5%
FeO; purple-blue stain). Several factors, including acidity and temperature of staining solution, affect the
color (hue) of the stain, indicating that a standard procedure must be followed if colorimetric techniques
are to be used in the determination of ferrous iron content in calcite.

INTRODUCTION the fabric of the rocks studied. In calcarenite,

Calcite containing small amounts of FeO is iron-free and ferroan calcites often occur in
called ferroan calcite ( P a l a c h e and others, 1951, sparry cement as layers only a few microns
p. 154). Staining techniques to distinguish iron thick, thus precluding standard analytic tech-
free calcite and ferroan calcite in thin section niques. Data can be obtained only with an elec-
are described in several recent papers (Fried- tron microprobe, and then with considerable diffi-
man, 1959; Evamy, 1963; Dickson, 1965). This culty.
procedure has been expanded so that the stains METHODS
from the surface of a rock also can be t r a n s f e r -
red to an acetate 1,'el (Katz and Friedman, The present work was done on calcite-filled
1965: Davies and Till, 1968). Stained peels are veins in septarian concretions. This calcite con-
less time consuming to prepare than thin sec- tains a wide range of iron values and occurs in
tions, hut show details of zoning with less clar- hands t h a t are thick enough so that petro-
ity. graphic and microprobe analyses can be com-
The commonly used stains act independently. pared, something that is not generally possible
Alizarin red-S stains calcite red, whereas potas- in limestones. Using a standard color reference
sium ferricyanide reacts with ferrous iron to we have compared the color of stains of both
form a blue stain. W h e n these dyes are com- thin sections and peels with the iron content of
bined, they stain ferroan calcite a color com- the stained thin sections as determined with the
posed of red and blue. Evamy (1963) suggested microprobe. For this reason accurate recognition
that as iron content increases the stain would of colors is essential. Terminology used follows
shi ft from red to mauve to purple. the Munsell system2 This system was used be-
The value of differentiating iron-free and cause ( a ) the Munsell colors are very consis-
ferroan calcite has been demonstrated in several tent, ( b ) the colors are quite close to those of
studies of limestones (Evamy, 1969; E v a m y and the stains, and (c) because most geologists are
Shearman, 1965; Davies and Till, 1968; familiar with the Munsell system which is used
Knewtson and Hubert, 1969). F o r example, ob- in the Rock-Color Chart ( G o d d a r d and others,
scure diagenetic features such as sequences of 194.8).
pore-filling calcite are readily apparent when Color is determined by several factors. Hue
iron-free and ferroan calcites are differentiated. refers to the attribute which determines the
To date, there has been little attempt to quan- '-'MunselI Book of Color obtainable from Munsell
titatively determine the amotmt of FeO in fer- Color Co. (2441 N. Calvert St., Baltimore, Md.
roan calcite by staining. This is in part due to 21218). In addition a color chart has been specially
prepared for use in determining FeO content by
Manuscript received July 19, 1971; revised Oc- color of stains. For information write "Color Chart,"
tober 25, 1971. P.O. Box 10111, Alexandria, Virginia 22310.
240 .VOTES

name in everyday speech. Ten major hues are we have followed is a modification of that used
recognized and each is divkled into ten numeri- by Evamy (1963) and Katz and Friedman
cal divisions. The major hues used in this paper (1965). The solution is prepared by dissolving 1
are red (R), red-purple ( R P ) , purple ( P ) , and gm alizarin red-S and 5 gm potassium ferri-
purple-blue ( P B ) . Color value indicates the cyanide in one liter of 0.2% HC1 (998 ml dis-
lightness or darkness of a color in relation to a tilled water containing 2 ml concentrated HC1 ).
neutral gray scale, which extends from absolute A slab of rock is cut and one surface ground
black to absolute white. The value symbol 0/ is with carborundum powder to at least 800 grit.
used for absolute black; the symboI 10/ is used The polished surface is etched in 2% HC1 (98
for absolute white. Values used in this work are ml distilled water containing 2 ml concentrated
6/ and 7/. Chroma indicates the degree of de- HC1 ) for about 20 seconds, and then immersed
parture of a given hue from a neutral gray of in the staining solution at room temperature for
the same vahte. The scale of chroma extends 4 minutes. The slab is removed from the solu-
from /0 (neutral gray) to /14 or further as tion and washed with distilled water making
strength (saturation) increases. Chroma values sure the surface is not hit by a direct flow of
used in this work range between /6 and /12. water or touched by fingers. The sample is al-
Each color has elements of hue, value and lowed to drain, but not become dry. This is quite
chroma, and is described by a notation com- important. If the sample is too wet the acetone
posed of three numbers and a letter. on the rock surface is diluted and a good peel
The procedure for staining acetate peels that can not be obtained ; if too dry the stain will not

o •

0 3.0
i °o •

|o IH
~iUllUUiUlKIIIIBIHIfllHU IInlHI IlUr~HIIHUlHII • Hi ilflflilHi nHlUlII|IIHlil
| |
! eeoc0 0 !
2.0 Z o E
,4-.I E • o S

C __,, Iii
~OHM~MI411HIIle0114ll IIIIIIII NI I INIIHIII~IIII llliR Igll IIUllllllnUllllll I Inl I l l U n d
°
i° ~ i•
1.0 i= °°
@0 ~ II • Peel
i o ° ,o0 I i QThinSeetion
HN4/qHMmHIMINfl~ m;muuolNtflmi

0.0 t ~ AI ' ~ Io
I I l I I I i I ! !

IOR 7.SR SR 2.5R 10RP 5RP 2.5RP 7,5P 5P 2.5P IOPB 7.5PB
4- Red .-~ 4 - R e d Purple -~- Purple -~4- P u r p l e Blue-4~

Color
FIG. l.--Ferrous-iron content plotted against stain color of thin sections and peels.

Calcite Phase Percent FeO Color of Stain

Non-ferroan calcite 0,0 Red (10R 6/12 to 2.5R 6/12)
Ferroancalcitel 0.5 to 1.5 Red-purple (10RP 6/12 to 2.5RP 6/10)
Ferroan calcite II 1.5 to 2.5 Purple (7.5P 6/10 to 2.5P 6/8)
Ferroan calcite III 2.5 to 3.5 Purple-blue (10PB 6/8 to 7.SPB 6/10)
 Ar 0 T E S 241

TABLE 1.--Factors that affect color qf sta~n (with blue filter) with the snhstage condenser
in and diaphragm open so that cleavage and
Factor Analysed Results crystal outlines are barely visible. This allows
more light than is normally used to pass through
Acidity of stain- High concentrations (0.4-0.8~
ing solution HC1) increase color intensity the microscope and is necessary to reduce sur-
and shift color toward a more face effects caused by irregularities on the thin
blue hue. Lower acidity (0.05% section or peel. F o r consistent results the exter-
HCl) has the opposite effect. nal light source on the color reference mnst be
Temperature of Warm solntions (40°C.) produce standarized. W e have used one 250 watt, 3,200 °
staining solution more bluish hues, as well as K General Electric lamp, placed 3 feet above
more intense and less uniform the color reference. Natural and overhead light
colors than solutions at room are eliminated.
temperature (23°-25 ° C.).
The microprobe analyses were conducted on
Dilution of stain- 250 ml of solution stains 30 stained thin sections with an A R L - E M X - S M
ing solution by use square inches of rock surface electron microprobe. The crystal detectors used
without significant changes in were LIF, A D P and RAP. All analyses were
color. Further use results in less
intense colors. carried out at 15 kv acceleration potential and
0.1 /,a sample current. The beam current was in-
Length of time rock Immersion times between 3 and tegrated against time in order to reduce the
surface is left in 6 minntes produces similar effects of t?eam drift. Chemically analyzed car-
staining solution colors. Shorter times (less than
3 minutes) result in reduction of bonates were used as standards. T h e elements
color intensity, whereas longer sought were Fe, St, Mg, Sr, Mn, and A1. At
times (greater than 6 minutes) least twenty five 10-second counts were taken
result in more intense colors and on each phase. Background corrections were ap-
excessively thick stains which
tend to crack on drying. plied to the raw data. Accuracy should he better
than ± 10% of the amount present.
Shelf life of Solutions start to decompose
solution within several days. RESULTS

Several factors, other than iron content, af-

fect the color of stains. Factors related to tech-
t r a n s f e r to the peel. The nearly dried surface is nique were analyzed separately using a sample
immersed in acetone and immediately pressed containing three distinctly different and rela-
down on a sheet of 1/16 inch acetate lying on a tively homogeneous calcite phases. T h e results
paper towel to absorb excess acetone and keep it summarized in Table I, show some factors (e.g.,
from flowing on the undersurface of the ace- high acidity and high t e m p e r a t u r e s ) change the
tate. The slab is pressed firmly onto the acetate hue of the stain, while others (e.g., low acidity,
without sliding it over the smooth surface. The prolonged use of solution, and too short immer-
sample is then tilted to pour off excess acetone sion times) reduce the intensity ( c h r o m a ) to a
and pressure is applied for an additional 10 sec- point where hue is difficult to determine. Both
onds. A f t e r several minutes the peel can be results are undesirable, indicating that the tech-
stripped from the rock. nique we have outlined should be followed
The procedure for staining thin sections is es- closely ff one wishes to nse our color references
sentially the same as that for preparation of to estimate FeO content in ferroan calcite.
stained peels. T h e thin section is etched and T h e orientation of calcite crystals with re-
then immersed in the staining solution. A f t e r spect to the stained surface and the presence of
four minutes the thin section is removed from elements other than iron were also considered.
the staining solution and the surface rinsed with Orientation does not seem to have any signifi-
distilled water. T h e wet thin section is examined cant effect on the hue of the stain, although it
under plane-polarized light with a petrographic does alter the intensity slightly. Manganese is
microscope. The slide should be periodically im- the only element analysed with the microprobe
mersed in distilled water, because when dry, the which might affect the hue. It was absent or
color of the stain is difficult to determine accu- present in trace amounts and does not seem to
rately. T h e colors of corresponding areas of be a factor in determining the color of the stain.
stained thin sections and stained peels are very W h e n iron content and stain color of both thin
similar with no systematic variations. sections and corresponding areas on peels are
Colors of stains are determined by visual plotted on a scatter diagram (fig. 1) there is an
comparison with a standard reference. T h e obvious trend such that h i g h e r iron values are
stains are examified in plane-polarized light associated with more bluish hues. T h e r e is
242 N 0 TEN

some deviation from a simple straight-line rela- premature and would only add confusion to the
tionship. This is in part due to our inability to literature. No values of FeO greater than 3.5%
exactly match areas analvzed by the microprobe were observed. T h e difficulties involved in dif-
with areas analyzed by (he petrographic micro- ferentiating the color of stains preclude a fur-
scope. This problem is complicated by grada- ther breakdown of the different types of calcite
tional changes in iron content from one area to with respect to color and FeO content.
a n o t h e r and zoned (with respect to iron con- Regardless of the terminology we conclude
t e n t ) calcite crystals. Another difficulty is in the that if proper care is taken d u r i n g preparation
observers' inability to differentiate clearly be- of stained thin sections or peels, the color can
tween colors of slightly different dues. be used for semiquantitative determination of
Despite these problems we find it useful to the FeO content of the calcite.
suggest a division into four different calcite
ACKNOWLEDGMENTS
phases (fig. 1 ). They are (1) n o n - f e r r o a n cal-
cite (0.0% F e O ) , ( 2 ) ferroan calcite I (0.5% W e t h a n k E. G. Kauffman, of the U. S. Na-
to 1.5% F e O ) , (3) ferroan calite lI (1.5% to 2.5 tional Museum, for the use of several samples
li'eO), and (4) ferroan calcite l l I (2.5% to analyzed in this work. T h e manuscript for this
3.5% F e O ) . Roman numerals designating the paper was read by L. I. Briggs, J. J. Fahey, K.
various ferroan phases refer to the mean FcO J. M n r a t a and T. R. W a l k e r and we appreciate
value. Any more formal nomenclature would be their criticisms and comments.

REFERENCES
DAVIES, P. J., aND TILL, R., 1968, Stained dry cellulose peels of ancient and Recent impregnated carboi~ate
sediments: Jour. Sed. Petrology, v. 38, p. 234--237.
DICKSON, J. A. D., 1%5, A modified staining technique for carbonates in thin section: Nature, v. 205, p. 587.
EVAMY, B. D., 1963, The application of a chemical staining technique to a study of dedolomitization : Sedi-
mentology, v. 2, p. 164-170.
, ANn SHEARMAN, D. J., 1965, The development of overgrowths from echinoderm fragments: Sedi-
mentology, v. 5, p. 211-233.
, 1969, The precipitational environment and correlation of some calcite cements deduced from artifical
staining: Jour. Sed. Petrology, v. 39, p. 787-793.
FR~EDMat¢, G. M., 1959, Identification of carbonate minerals by staining methods: Jour. Sed. Petrology, v.
29, p. 87-97.
GODBARD, E. N., TRASK, P. D., DEFORD, R. K., RovE, O. N., S~I~GEWaLD, J. T., aI, rD OVERBECK, R. M.,
1948. Rock Color Chart: National Research Council Washington, D.C. (republished by Geol. Soc.
America, 1951), 6 p.
KATZ, A., AND FRrEDMAI'q G. M., 1965, The preparation of stained acetate peels for the study of carbonate
rocks: 1-our. Sed. Petrology, v. 35, p. 248--249.
KNswTSOlq, S. L., AXD HUBERT, J. F., 1969, Dispersal patterns and diagenesis of oolitic calcarenites in the
Ste. Genevieve Limestone (Mississippian), Missouri: J-our. Sed. Petrology, v. 39, p. 954-968.
PaLACI-IE, C., BERMAN, H., AND FRONImI., C., 1951, Dana's System of Mineralogy, 7th ed. : Wiley, New York,
vol. 2, 1124 p.

A USEFUL VOLUMETER 1

N. C. J A N K E
Department of Geology, Sacramento 'State College, California 95819

ABSTRACT
A micrometer caliper, modified by the addition of a needle-tipped extension rod and removal of part of the
frame, is the basis of a simply constructed, useful volumeter. Different :tubes may easily be used, allowing
each particle of a wide range of sizes to be measured with the same pre-specified precision.

INTRODUCTION to fit into the cup of an air comparison pycnom-

W h e n it was necessary to find the individual eter on hand, the simple volumeter described be-
volumes of many particles which were too large low was constructed and found to be very useful.
At first an overflow volumeter similar to that
I Manuscrlpt received May 17, 1971; revised An- described by Schurecht (192~) was constructed
gust 18, 1971. and used, but the very slow draining needed for