Stdimentology (1983) 30,579-583

Chemical controls of cathodoluminescence of natural dolomites and

calcites: new data and review

IAN J. FAIRCHILD
Department ofGeologica1 Sciences, University of Birmingham
P.O. Box 363, Birmingham B15 2TT. U.K.

ABSTRACT

Calcites and dolomites from the late Precambrian Bonahaven Formation of Scotland exhibit luminescence
when MnC03>0.03 wt % (dolomite) or >0.06 wt % (calcite) and FeCO, <2-2.5 wt % (dolomite).
Comparison with other published data shows close similarity in the position of Fe-quenching in dolomite,
but more variability in the position of Mn-activation in calcites and dolomites and the onset of Fe-
quenching in calcites. These anomalies are thought to relate to chemical controls subsidiary to the
dominant factors of Fe and Mn concentration. It is not practical to make a useful comparison between
operating conditions of different luminescence instruments because of differences in design and an inability
to measure routinely the current actually on the specimen surface.

INTRODUCTION crystals from member 3 (Fairchild, 1978). Calcites

Following the recent publications by Pierson (198 l),
Richter & Zinkernagel (1981) and Frank, Carpenter
& Oglesby (1982) with data on Fe and Mn control of
cathodoluminescence in dolomites and calcites, fur-
ther observations are presented below and their
significance discussed. These publications together
with Marfunin (1979, chapter 5) provide a review
of the literature indicating that Mn activates catho-
doluminescence in natural carbonates and that the
dominant quenching agent is ferrous iron.
METHODS
The samples studied are from the late Precambrian
(Vendian) Bonahaven Formation of Islay, Scotland.
Dolomite data were obtained from: (1) penecontem-
poraneous fine-grained dolomites from member 3 of
this Formation (Fairchild, 1980a), (2) burial diage-
netic dolomite from member 1 (Fairchild, 1980b) and
(3) isolated, presumed burial diagenetic dolomite
00374J746/83/08004579$02.00
01983 International Association of Sedimentologists
studied were various pre- and syn-tectonic crystals in
members 3 and 4 (Fairchild, 1978).
Chemical analysis was performed by electron
microprobe. Operating conditions were : accelerating
voltage 15-16 kV, specimen current 380 nA, beam
size 4 4 5 pm (focused), specimen scan mode (usually
at 10 ~ r min-
n ') and carbonate standards. Calculated
detection limits for FeC03 and MnCO, are 0,004
wt %; estimated precision is f 10% of the analysis.
Further details are given in Fairchild (1980b).
Cathodoluminescence was achieved using a non-
commercial cold-cathode instrument of conventional
design built in the Department of Geology, Not-
tingham University. An accelerating voltage of 30
kV, current of 0.64.8 mA (incorrectly stated in
Fairchild, 1980b) and a beam area of 100 mm2 was
applied to polished thin sections. Identical observa-
tions of selected samples were later made on a
different cold-cathode instrument at Birmingham
University using 15 kV,0.2 mA and a beam area of
1.5 mm2. Difficulties in comparing the operating
conditions of different luminescence instruments are
discussed later.
The data presented represent a substantial fraction
of published information on this topic, although they

5 79
580 I . J . Fairchild

were not obtained under ideally controlled conditions.
Thus only the subjective distinction of bright, dull
and no luminescence was made. Many samples with
apparently homogeneous luminescence proved chem-
ically inhomogeneous on the scale of a few microns,
so they are represented by lines rather than points on
Mn-Fe plots. Other samples exhibited finely zoned
crystals where the characterization of each zone was
less accurate than for homogeneous crystals, but still
plottable as points on a diagram with logarithmic
scales. Despite these deficiencies, fields of luminesc-
ence and noluminescence can be clearly distinguished.
RESULTS
Dolomite data are plotted on Fig. 1 and calcite data
on Fig. 2. Where possible the approximate boundary
between dull and no luminescence (luminescence-
limiting line) is drawn in.
In Fig. 1 the orientation of the Fe-quenching line is
not completely constrained by the data points, two
end-member possibilities being shown which place
an equally small number of observations on the
wrong side of the line. The vertical possible Fe-
quench line shown is at 2.4 wt % FeCO, . At lower Fe-
concentrations luminescence is activated by MnCO,
concentrations greater than about 0.03 wt %. There
are insufficient data to determine the form of the
luminescence-limiting line in the lower right of Fig. 1.
Figure 2 shows that luminescence persists at least
up to 1 wt % FeCO, in the calcites studied. A
concentration of MnC0, greater than about 0.06 wt
% seems necessary to cause luminescence.
DISCUSSION
There is close agreement between the vertical Fe-
quenching line of Fig. 1 and that of Pierson (1981)
who has a vertical line at about 2.7 wt % FeCO,. It
should be noted that Piersons data are not constrained
to a vertical Fe-quench line (see Fig. 4). The data of
other workers (Fig. 3) are also closely comparable.
Evidence from the data of Churnet & Misra (1981)
and in particular Frank (1981) plotted on Fig. 3
supports a non-vertical Fe-quench line since luminesc-
ence is enhanced by increasing Mn at constant Fe
values. Richter & Zinkernagel (1981, p. 1279)
reported a weakening of luminescent intensity in
dolomite above about 2 wt % FeCO, but a persistence
of faint luminescence up to greater than 10 wt %
FeCO,. These high-Fe dolomites have 0.2-1 wt 2
MnCO, (Richter, 1982, personal communication).
This observation could represent enhanced luminesc-

wt % w I. %

- - - II
MnCO, Mn 0.

I 35
.9
LUMINESCENCE

0 5

I.
01

_--
01 0 0 5

005

3 01 .... ......
4
0 0 5 01 0.5 I wt%Fe 5
0 01

-
005 01 0.5 I wt %FeCO, 5 10
Homogenous Inhomogenous
KEY chemistry chemistry
8right luminescence
Dull luminescence m --. - - -- Approximate limiting
lhne o f luminescence
No luminescence A

Fig. 1. Fe-Mn chemistry and luminescence for dolomites from the Bonahaven Formation.
 Chemical controls of cathodoluminescence 58 1
Wt% W l %
ence generated by the hot-cathode instrument (Zink-
ernagel, 1978) used by these authors.
Given the overall similarity in the atomic structures
of calcite and dolomite and the explanation of charge-
transfer absorption by Fe for its quenching behaviour
(Marfunin, 1979), one would expected Fe-quenching
in calcite too. Frank et al. (1982) showed that the
occurrence of Fe-quenching is dependent on Mn-
composition in calcite although no completely
quenched samples were analysed. They suggested that
-6
A X contours of brightness are straight lines at 45" to the
005-
Fe and Mn axes (e.g. Fig. 4), and that samples with
Bb B B P
.4 NO LUMINESCENCE Fe/Mn > 2 show only dull luminescence. This infor-
.o 01 mation is contradictory to that of Fig. 2 (which
indicates bright luminescence at least up to Fe/Mn = 5)
0 0s 0.1 0 5 w l % Fe and the data of Pierson (1981) where bright luminesc-
0 01;
ence is exhibited by calcite with 2 wt % FeC0, and
0.2 wt % MnCO,. Could the difference be due to
experimental techniques? This seems unlikely since
Frank et al. (1982) used the same methods as Frank
(1981) who obtained results consistent with other

I .L0.5

05- LUMINESCENCE

7 /

-0.1

0 1.-0-05
I '

0 051
NO
LUMINESCENCE

Bright luminescence o o ' ] " ' ~ ~ ?I , 0,,5 ! w t 7- F;

0 005
Dull luminescence
01 05 I w i "/- FeCO, 5 10
1 NO luminescence

00110005 . 005 01 05 I wl % Fe Fig. 4. Summary of luminescence-limiting lines from data of

005 01 0 5
Fig. 3. Collation of other published data for dolomite.
l = F r an k (19811, 2=Churnet & Misra (1981), 3=Ebers &
Kopp (1979),4=Choquette & Steinen (1980). The solid line
is an approximate luminescence-limiting line from Frank's
(198 I ) data. The dashed lines are the luminescence-limiting
lines of Fig. 1 for comparison.
I 5 WI % FeCO, Pierson (1981), Frank (1981), Frank et al. (1982), Richter &
Zinkernagel (1982) and herein. Dolomite: 1, 2 alternative
lines from the data of Fig. 1; 3, 4 alternative lines from the
data of Pierson (1981); 5 , line from data of Frank (1981);
Calcite:6 , Mn activationline fromdataof Fig. 2; 7, boundary
of moderate and dull luminescence (Frank et al., 1982); 8 ,
Mn-activation line for calcite and dolomite (Richter &
Zinkernagel, 1982).
582 I . J . Fairchild
cold-cathode-users as discussed above. Thus a real
difference in behaviour between different suites of
calcites seems likely.
One can infer that the observational conditions
used by myself and Pierson (1981) seem to be
effectively similar since our dolomite Fe-quenching
lines lie close together. Hence one would expect
comparable results also for Mn-activation at low Fe-
concentrations. However, Pierson (1981) reported
bright luminescence in dolomite and calcite with as
little as 0.021 wt % MnCO,, and he refers in passing
to unpublished data suggesting activation in dolomite
at around 0.017 wt % MnCO,. Richter & Zinkernagel
(1982, p. 1280) reported Mn-activation at around
0.008 wt % MnCO, in calcite and suggested (on the
basis of two analyses) a similar figure for dolomite.
Even if one excludes the figures of Richter &
Zinkernagel (1982) from comparison in case their
effective experimental conditions differ from other
authors, discrepancies exist between authors in Mn-
activation in dolomite and calcite and in the onset of
Fe-quenching in calcite which are not obviously
attributable to differences in these conditions. Differ-
ences in Mn-activation could relate to varying lattice
sites or oxidation states or Mn, or more likely to the
presence of trace quantities of other ions acting as
activators or sensitisors. Differences in quenching
behaviour might relate to the presence of small and
varying amounts of Fe3+ in solid solution in the
carbonate lattice since Marfunin (1979) has stated
that Fe3+ is a more effective quenching agent than
Fez+.
The current state of knowledge allows the following
deductions about dolomite and calcite chemistry from
cathodoluminescence. For dolomite, absence of lu-
minescence will normally be due to high Fe or low Mn
(or both, although this case seems rare). Routine
potassium ferrityanide staining will allow the high-
Fe case to be distinguished, but it should be
remembered that dolomite stains more slowly than
calcite. Thus the blue colour visible in transmitted
light in thin section for calcite with say 1% FeCO,
after a given staining time (e.g. Dickson, 1966;
Lindholm & Finkelman, 1972)will be far more intense
than for a dolomite with say 1-2% FeCO,. However,
in my experience the dolomite hand specimen will
show a distinct colour change. No precise maximum
Mn-concentration can be inferred if Fe is low,
although Fig. 4 indicates some possible values. The
same general statement applies too to calcite, although
the onset of Fe-quenching seems more variable here.
This sort of reasoning was used by Meyers (1974).
However, it must be stressed that if a precise
knowledge of mineral chemistry is needed for petro-
genetic studies, then a chemical analysis (preferably
by microprobe for inhomogeneous or impure samples)
should be carried out.
Marshall (1978) suggested that various details of
experimental conditions of cathodoluminescence be
stated to allow comparison between different pub-
lished papers. The similarity of observations on Fe-
quenching in dolomite noted earlier suggest that the
experimental conditions do not vary drastically be-
tween different workers, although this may not apply
to the hot-cathode instrument of Zinkernagel (1978)
and Richter & Zinkernagel(l982). It is my contention
that it is of no practical use to attempt to define the
experimental conditions as closely as Marshall (1978)
suggested. This is because there are certain unquan-
tifiable variables. For example, the design of the
cathode tube varies between instruments ;for a precise
comparison one would need to know the current on
the specimen surface, but it is impractical to perform
such measurements routinely. Another factor is that
the efficiency of any given apparatus will vary from
time to time depending on whether optimum vacuum
conditions are maintained. Also the loss of light
(which varies with different microscopes) from speci-
men to camera cannot be readily quantified and also
varies with discolouration of the chamber window.
Until the time when a set of standards of given
luminescent intensities are circulated to all users and
photographed along with specimens studied, no
meaningful comparison can be made. However, since
the usefulness of cathodoluminescence in sediment-
ology is primarily to interpret textures, this lack of
standard samples is not of crucial importance.
CONCLUSIONS
Using a cold-cathode instrument under typical con-
ditions, the onset of activation of cathodoluminesc-
ence in dolomite occurs at concentrations of Mn in
the range of 0.015-0.03 wt % MnCO,. Iron-quenching
occurs within the interval 2-3 wt % FeCO, and
appears to be partly dependent on Mn content.
Insufficient data are available to determine the precise
shape of the luminescence-limiting line.
In calcite, activation occurs at <0.02 wt % MnCO,
(Pierson, 1981) to 0.06 wt % MnC0,. The onset of Fe-
quenching appears to differ between different rock
suites and requires further documentation.
Although the concentrations of ferrous iron and
 Chemical controls of cathodoluminescence
Mn are the dominant factors in determining the
presence of cathodoluminescence in natural carbon-
ates, other chemical factors appear to play a secondary
role.
ACKNOWLEDGMENTS
Acknowledgment is overdue to Mr W. Wilson who
built the Nottingham cathodoluminescence instru-
ment. I am grateful to Dr J. V. P. Long for discussion,
Drs J. A. D. Dickson and W. J. Meyers for
commenting on the manuscript and my wife Sue for
translations. Analyses were performed during the
tenure of a NERC studentship at Nottingham
University.
REFERENCES
CHOQUETTE, P. W. & STEINEN,R.P. (1980) Mississippian
non-supratidal dolomite, Ste. Genevieve Limestone, Illi-
nois Basin : evidence for mixed-water dolomitization. In :
Concepts and Models of Dolomitization (Ed. by D. H.
Zenger, J. B. Dunham & R. L. Ethington). Spec. Publs
SOC.Econ. Paleont. Miner., Tulsa, 28, 163-196.
CHURNET, H.G. & MISRA,K.C. (1981) Genetic implications
of the trace element distribution pattern in the Upper
Knox carbonate rocks, Copper Ridge district, E. Tennes-
see. Sedim. Geol. 30, 173-1 94.
DICKSON, J.A.D. (1966)Carbonate identification and genesis
as revealed by staining. J . sedim. Petrol. 36,491-505.
EBERS,M.L. & KOPP, O.C. (1979) Cathodoluminescent
microstratigraphy in gangue dolomite, the Mascot-Jeffer-
son City district, Tennessee. Econ. Geol. 74, 908-918.
FAIRCHILD, I.J. ( I 978) Sedimentation and post-depositional
history of the Dalradian Bonahaven Formation of Islay.
Unpublished PhD. thesis. University of Nottingham.
4 FAIRCHILD, I.J. (1980a) Sedimentation and origin of a Late
Precambrian dolomite from Scotland. J . sedim. Petrol.
50,423-446.
FAIRCHILD, I.J. (1980b) Stages in a Precambrian dolomiti-
zation, Scotland : cementing versus replacement textures.
Sedimentology, 21,631-650.
(Manuscript received 8 January 1982; revision received I7 December 1982)
583
FRANK,J.R. (1981) Dedolomitization in the Taum Sauk
Limestone (Upper Cambrian), Southeast Missouri. J .
sedim. Petrol. 51, 7-18.
FRANK,J.R., CARPENTER, A.B. & OGLESBY, T.W. (1982)
Cathodoluminescence and composition of calcite cement
in the Taum Sauk Limestone (Upper Cambrian), South-
east Missouri. J . sedim. Petrol. 52, 631-638.
LINDHOLM, R.C. & FINKELMAN, R.B. (1972) Calcitestaining:
semiquantitative determination of ferrous iron. J . sedim.
Petrol. 42, 239-242.
MARFUNIN,A.S. (1979) Spectroscopy. Luminescence and
Radiation Centers in Minerals. Springer-Verlag, Berlin. 352
PP.
MARSHALL, D.J. (1978)Suggested standards for the reporting
of cathodoluminescence results. J . sedim. Petrol. 48, 65 1-
653.
MEYERS, W.J. (1974) Carbonate cement stratigraphy of the
Lake Valley Formation (Mississippian) Sacramento
Mountains, New Mexico. J . sedim. Petrol. 44,837-861.
PIERSON, B.J. (1981) The control of cathodoluminescence in
dolomite by iron and manganese. Sedimentology, 28, 601-
610.
RICHTER, D.K. & ZINKERNAGEL, U. (1981) Zur Anwendung
der Kathodolumineszenz in der Karbonatpetrographie.
Geol. Rdsch. 10, 1276-1302.
ZINKERNAGEL, U. (1978) Cathodoluminescence of quartz
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NOTE A D D E D I N PROOF 1
Amieux (1982) explores the possibility of using
cathodoluminescence colour as well as intensity as a
geochemical indicator of the environment of crystal-
lization since colour may often relate to different
oxidation states or lattice sites of Mn and Fe. More
fundamental research is urgently required to develop
this promising application of cathodoluminescence.
AMIEUX,P. (1982)Lacathodoluminescence : mtthodedetude
stdimentologique des carbonates. Bull. Centres Rech.
Explor.-Prod. Elf-Aquitaine, 6,437-483