Geochimica et Cwmochimka Acts, 1999, Vol. 33, pp.

997 to 199% Pergamon Prew Printed in Northern Ireland

NOTE!3

Carbon-13fractionation between aragonite and calcite

MI~EAEL RWINSON
Department of Chemistry, The University of Chicago, Chicago, Illinois 60637

and

ROBERT N. CLAYTON
Enrico Fermi Institute, and Departments of Chemistry and Geophysioal S&noes
The University of Chicago, Chicago, Illinois 60037

in revisedform 15 April 1989)

(Received30 August 1968; acoe~~ted

&&a&-Ar8gonite and caloite were precipitated from bicarbonate solutions by slow removal
of oarbon dioxide at 26°C. Carbon isotope fractionation faotors (expressed as 1000 Ina) are:
oaloite-bicarbonate ion 0.9 f 0.2; aragonite-bicarbonate ion 2.7 f 0.2; aragonite-oalcite
1.8 f 0.2. Theoretical oalculation of the aragonite-oalcite fractionation gives 0.9.

TARUTANI et al. (1969) have shown that aragonite concentrates O’s relative to calcite at 26°C
by a small factor. This fraotionation is in reasonably good agreement with the result of a cal-
culation based upon an extension of the Urey-Bigeleisen-Mayer treatment. As a further test
of the applicationof the theory to solid phases, we have measuredthe carbon isotope fractionation
between the same two phases. There are several published sets of vibration81 frequenoies
for the oarbonate ion in calcite and aragonite (HEXTER, 1968; MILLERet al., 1960; HUANQ
and Tuna, 1960; ADLER and KERR, 1963; WEIR and LIPPINCOTT, 1961; SCHROEDER et al.,
1962; Ross and GOLDSMITH,1964). Preliminary calculations with some of these frequencies
yielded the surprising prediction that the equilibrium carbon isotope fractionation factor
between aragonite and calcite at 25” might be as large as 1.00’7. It appeared therefore that an
experimental determination of this factor would permit selection of the best set of vibrational
frequenoies.
It wae neoessary to make one sign&cant modification of the experimental procedure used
by T~LRUTANI et al. (1969) in precipitation of aragonite and calcite for oxygen isotope measure-
ments: that is to provide in the solution a carbon reservoirwhich is large relative to the amount
of carbonate and oarbon dioxide to be removed. This ~8s accomplished by adding sodium
bicarbonate in about lOO-fold excess over the calcium carbonate. The conoentration of bi-
carbonate ion was varied by a factor of 1.4 to give a variation by a factor of 2 in calcium con-
centration in the starting solutions.
Aragonite was produoed by adding magnesium chloride to the solution. Both calcite and
aragoniteprecipitationswere carriedout in solutionsmade up to ionic strength of 0.5 by addition
of sodium chloridein order to maintain a nearly constant ionio environment during the course of
the precipitation of calcium carbonate and the removal of carbon dioxide.

EXPERIMENTAL
PROCEDURE
One liter solutions were made up with compositionsgiven in Table 1, and 250 mg of reagent
grade calcium carbonate was added to each. Carbon dioxide gas was bubbled through the
7 997
99x Sates

solutions for four to five hours, until the solution was saturated with CO, gas. Each solution
was then allowed to equilibrate overnight, filtered to remove the excess CaCO,, and again allowed

Table 1. Compositions of starting solutions (concentrations in millimoles/l)

Run number N&l NaHCO, M&q Ionic strength

-______ ---. .-- ._~ _.~___ _ ~~_ ___~.___
Cl 328 12; 0.455
c2 328 1*7
I 0.455
c3 420 HO 0.500
Al 300 127 9 0.466
A2 300 127 9 0.455
A3 390 80 10 0.500
__

to stand overnight to assure isotopio equilibrium among the dissolved oarbon species. About
500 ml of each solution was placed in a gas washing bottle in a water bath at 25°C and ?i,
was bubbled through the solution at the rate of 2-5 calmin. Precipitations were run in pairs
(one aaloite and one aragonite) with the same nitrogen flow rate and reaction time.
At the beginning and end of precipitation, the pH of the solution was determined, and the
concentration and isotopic composition of total dissolved carbon were measured. To determine
the oarbon-13 abundance, a 2 ml aliquot was placed into a bulb with a sidearm containing 5 ml
of 100 % I+,PO,. The bulb was attached to a vacuum system but not pumped on. The aliquot
in the bulb was frozen with liquid nitrogen and the air pumped out of the system. The solution
was then melted, reacted with the aoid, and frozen with a dry ice bath. The CO, was extracted
and collectted; the solution was melted, refrozen, and the CO, again extraoted. Isotopic
composition of the CO, was determined on a double-collecting rnw spectrometer.
After from two to four days, the precipitated CaCO, from each solution was collected,
filtered, washed with water and acetone, and dried. The crystals were examiaed under a micro-
scope to determine their identity as aragonite or calcite by morphology and refractive index.
The identification was verified by X-ray diffraction. A portion of the solid oarbonate was reacted
with 100 ‘A qPO4 and the resulting CO, ~a.3 analyzed mass speatromatriaally.

EXPERIMENTAL RESULTS
The results of the experimental measurements are given in Table 2. Carbon isotope aomposi-
tions are in the 6 notation, relative to the Chicago PDB standard, and have been corrected for
mass spectrometer valve mixing, background, mass-44 tail and for 01’ content (CRAIU, 1957).
Some uncertainty is involved in evaluating the isotopic composition of the bicarbonate ion
in solution. Its oomposition changes during the experiment aa a result of (a) an increase of
SCzs for the total oarbon in solution due to loss of isotopically lighter CO,, and (b) a change in
proportionsof COs2-, HCOs- and CO, in solution due to increaseof pH. The abundances of the
carbon-containingspecies in solution were calculated from the measured values of pH and total
carbon content, using the values 6.36 and IO.33 for the first and second pK’s for carbonic acid.
Activity aoeffioientsfor HCO,- and COs2- were taken from GARRELS et aE. (1961). The equilib-
rium constant for carbon isotope fractionation between bioarbonate ion and aqueous CO,
was taken as 1.0082 (VOGEL, 1961). The constant for carbonate ion-bicarbonate ion was
calculated from the values given by THODE etal. (1905) for bicarbonate ion-CO, gas and carbonate
ion-CO, gas. For this latter fractionation, they provided a lower limit of 1.0133, and a maximum
observed value of 1.0166. We have calculated our data using both of these factors. This
introduces a systematio unoertainty of about O*lyWin the estimates of fractionation of soIid
carbonaterelative to bicarbonateion, but the effect cancelsout in the estimation of the aragonite-
calcite fractionation.
For each experiment, a mean value of the bicarbonate isotopic composition was found by
averaging the initial and &al values. Since the change in bicarbonate isotopic composition is
small, no significant uncertainty is introduced by this process. The amount of change is also
variable from one experiment to another, but there appears to be no systematic relationship
to the isotopic fractionation factors. The resultingfractionations at 25”C, expressedEUY 1000 lna
are: aragonite-caloite 1.8 f 0.2; oak&e-bicarbonate ion 0,9 + 0.2; aragonite-bicarbonate
 Table 2. Results of precipitation experiments

Total diss.
carbon 6HCO,- dHCO,- 1000 ln a
RuIl Time (mmole/l) PH (a) (b) CeCOS-HCOa
No. (W Initial Filld Initial Find Initial Find Initial Final SC&O, (a) (b)

Cl 63 136 104 6.69 8.78 -31.03 -31.46 -31.03 -31.95 - 30.36 0.92 1.18
c2 66 128 114 6.96 8.00 -30.92 -31.02 - 30.92 -31.11 -30.12 0.86 0.92
c3 96 90.5 70 6.60 8*22 -31.08 -30.93 -31.08 -31.08 -30.30 0.72 0.80
Mean 0.83 0.97
Al 63 138 101 6.67 8.40 -31.24 -31.42 -31.24 -31.66 -28.60 2.82 2.93
A2 66 129 107 6.90 8.30 -31.57 -30.84 -31.67 -31.02 -28.62 2.77 2.86
A3 96 90.6 68.5 6.67 8.38 -30.91 -30.66 -30*91 -30.89 -28.43 2.42 2.66
Mt%lJl 2.67 2.78

(a) Using ~~~~~~~~~ = 1.0133.

(b) Using Kco,~-co~ = 1.0166.
1000 Xotes

ion 27 f 0.2. The error assigned to these fraction&ions is the average analytical error of the
measurements, and does not include any systematic errors, such as that due to departure from
equilibrium.
1hcuss1ox

Calculations of isotopic partition function ratios for aragonite and calcite were made using
an extension of the UREY (1947) and BIOELEISEN-MAYER (1947) theory as described by O'NEIL
et al. (1969). The same approximations were used in the calculations reported by C’PiEIL el ILL.
(1969) and TAXJTANI et al. (1969), i.e. internal vibrational degrees of freedom of the carbonate
ion were treated separately, using the fundamental frequencies as determined by infrared
spectroscopy, and lattice modes were treated by a single Debye function with 0 chosen to fit
the low-temperature hea.t capacity data, after subtraction of the vibrational contribution to the
heat capacity. Since these B’s are identical for calcite and aragonite (400”K), the difference
between their partition function ratios arises entirely from differences in the internal vibration
frequencies of the carbonate ion.
In the case of aragonite, the lower site-symmetry of the carbonate ion leads to a removal
of the degeneracy of rs and Ye, resulting in a splitting of the i.r. absorption peaks. In our cal-
culations, we used an average value of the observed frequencies, and applied a single value of the
isotopic shift factor, as determined by means of a HEATH and LINNETT (1948) force-field for a
symmetrical carbonate ion. These approximations probably introduce a smaller error than t,hat
associated with assigning a frequency to the broad and intense vs band (see below).
BOTTINGA (1968) found that the frequency data of SCI~ROEDER et al. (1962) gave the best
agreement with experiment for calcite-water and calcite-CO, isotope fractionations. The
frequencies used in the present work are given in Table 3. The symmetric stretching frequency
v1 does not contribute to carbon isotope fractionation. The frequencies are taken from SCHROEDER

Table 3. Vibrational frequencies and calculated partition function ratios at 25°C

Calcite Aragonitx
_
VI (cm-‘) 1070 1066
% 881 866
% 1460 1475
V4 712 708
In (Q13/Q1*) internal* 0.18308 0+18400
In (Q’8/Q’e) lattice 0.00216 0.00216
In (Q’8/Q12) total 0.18523 0.16615

* Reduced partition function ratios as defined by UREY (1947).

et al. with the exception of vs for aragonite, which was taken from ADLER and KERR (1963).
since no value was given by SCHROEDER et al. This is the same set of frequencies used by
TARUTANI et al. for calculation of oxygen isotope fractionations. The resulting isotopic partition
function ratios are given in Table 3. The calculated aragonite-calcite fractionation: 1000 lnu =
0.9 at 25°C.
CONCLUSIONS
The slow precipitation of caloite or aragonite from bicarbonate solutions appears to give an
equilibrium isotope fractionation for carbon as well as for oxygen. There is no proof that
isotopic equilibrium was attained in the experiments, but the insensitivity of the measured
fractionation to variations in solution concentration and precipitation rate make such an as-
sumption plausible. The possibility cannot be ruled out, however, that the factors which lead
to the precipitation of metastsble aragonite may also bring about a non-equilibrium isotopic
distribution. Such an effect might occur in nature as well.
According to our experiments, Cl3 is enriched in aragonite relative to calcite by l*S%, and
in calcite relative to bicarbonate ion by O-9%,. VOGEL (1961) gives experimental determinations
of carbon isotope fraction&ions of oarbon dioxide gas relative to bicarbonate ion and relative
to calcium carbonate (presumably calcite). These results yield a c&it+bicarbonate fractionation
 Notes 1001

of 1000 lna = 12 f 0.8 (22%). Combination of BAERTEICEI’S (1957) determination of a carbon

dioxide+al&e faotor of l*OlO with a CO,-HCOs- faotor of f-077 (Voorr~, 1961) yields a value
of 1000 Ina = 2.3. All of these values are compatible with the observations of CRAIG (1964)
that average limestones have 6C1s about 27&,greater than average oceanic bicarbonate.
KEITH et al, (1964) observed differences in 6018 and KY* between fibrous aragonite in ex-
ternal ligaments and shell carbonate (calcite or aragonite) in several marine and fresh water
peleoypods. The mean differences were enrichments in the aragonite of 05% for oxygen and
1.0% for carbon. These differences are similar to those seen in inorgsnio preuipitation of
aragonite and calcite at 25”, i.e. O*Sy&,for oxygen (TARUTA~Iet at., 1969) and 13yW for carbon
(this work). Although the natural pelecypod data are not simple aragonite-calcite differences
the coincidence of the results suggests a dominant control by equilibrium factors.
The agreement of the experimental aragonite-calcite fractionation with the theoretical
value is fair if the vibrational frequencies of SCHROEDER et al. (1962) are used, The serious
disagreementfound if other publishedfrequenciesare used arisesprincipallyfrom the rs frequency
of both calcite and aragonite. In all the other referencescited here, this frequency for oalcite is
given as about 1432 cm-r, whereas SCHROEDER et al. and Ross and GOLDSMITB. (1964) give a
value of 1460 cm-i. In room temperature spectra, this absorption is intense and very broad.
The liquid helium temperature measurements of SCHROEDER et aE. allowed a more accurate
determinationof the fundamental frequency. This single change of frequency produces a change
of 3*7x,, in the calculated partition function ratio at 25°C. This example shows that great
caution must be used in the application of theoreticallycalculated isotopic fractionationfactors.
Ac~w~ag~~-~. RUBINSONwas a participant in the National Science Foundation Under-
graduate Reseamh Program. The researchwas also supported by NSF Grant Number GA-614.

REVERENCES
ADLER H. H. and KERR P. F. (1963) Infrared absorption frequency trends for anhydrous
normal carbonates. Amer. Mineral. 42, 124-137.
BAERTSCHIP. (1957) Messuug und Deutung Relativer Ha~gkei~va~ationen von Or8 und
C!lsin K~bo~tges~~en und ~~eralien. S&we&r.~~~~~. P&ogr. &f&t. 37,73-162.
BI~ELEISENJ. and &vx~ M. G. (1947) Calculations of equilibrium oonstants for isotopic
exohange reactions. J. Chem. Phy8. 16, 261-267.
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GARRELSR. M., THOMSON M. E. and SIE~J~RR. (1961) Control of carbonate solubility by
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HEATR D. F. and LINNETT J. W. (1948) Molecular force fields-Part III-The vibration
frequencies of some planar XY, molecules. Tram. Faraday Sot. 44, 8733878.
HEXTERR. M. (1958) High resolution, ~mperature-dependent spectra of calcite. Spctrochim.
Acta 10, 281-290.
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311-324.
KEITHM. L., ANDERSONG. M. and EICHLERR. (1964) Carbon and oxygen isotopic composition
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MILLERF. A., CARLSONG. L., BENTLEYF. F. and JONES,W. H. (1960), Infrared spectra of
inorganic ions in the cesium bromide region (70~300 cm-r). S~~t~~h~rn. Aeta 16,135-235.
O’NEIL J. R., CLAYTONR. N. and MAYEDAT. K. (1969) Oxygen isotope fractionation in divalent
metal carbonates. In preparation.
Ross S. D. and GOLDSMITH J. (1964) Factors affecting the infrared spectra of planar anions
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Spectrochim. Acta 20, 781-784.
1002 Notes

SCHROEDEB R. A., WEIR C. E. and LIPPINCOTT E. R. (1962) Lattice frequencies and rotational
barriers for inorganic carbonates and nitrates from low temperature infrared spectrosoopy.
J. Rea. U.S. Nat. Bur. Stand. @A, 407-434.
I!.~R~TANI T., CLAYTON R. N. and MAYEDA T. K. (1969) The effect of polymorphism and
magnesium substitution on oxygen isotope fractionation between calcium carbonate and water.
Qeochim. Coamochim. Acta. 33, 987-996.
THODE H. G., SHIMA M., REES C. E. and KRISWAMURTY K. V. (1965) Carbon-13 isotope
effects in systems containing carbon dioxide, bicarbonate, carbonate, and metal ions. Can.
J. Chem. 48, 682-595.
UREY H. C. (1947) The thermodynamic properties of isotopic substances. J. Chem. Sot. (Lonthn~
562-581.
VOUEL J. C. (1961) Isotope separation factors of carbon in the equilibrium system CO,-HCO, .-
COs2-. In Summer Course on N&ear Geology, Varenna, pp. 216-221. Comitato Nazionale
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WEIR C. E. and LIPPINCOTT E. R. (1961) Infrared studies of aragonite, calcite and vaterite
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173-184.

Geochimica et Cosmochimica Acts, 1969, Vol. 33, pp. 1002 to 1006. Pergamon Preen. Printed in Northern Irelaod

Rubidium and strontium determinations by X-ray fluorescence

spectrometry and isotope dilution below the part per million level
B. W.
CHAPPEU
Department of Geology, Australian National University, Canberra, A.C.T.
Australia
and
W. COMPSTON, P. A. ARRIENS and M. J. VERWO~
Department of Geophysics and Geoohemistry, Australian National
University, Canberra, A.C.T., Australia

(Received 20 January 1969; accepted in revised form 17 March 1969)

Al&r&--The rubidium and strontium contents of dunite DTS-1 and peridotite PCC-1 and
of rubidium in a standard pyroxene Px-1 have been measured by X-ray fluorescence speotrom-
etry and by isotope dilution. Both techniques are useful in determining low concentrations
of these elements.

THIS paper arose from a study of the rubidium and strontium contents of several standard rock
and mineral samples, with the aim of comparing results obtained by X-ray fluorescence spec-
trometry and isotope dilution. Because of the low contents of rubidium and strontium in the
standards DTS-1 (dun&e) and PCC-1 (peridotite) (FLANAGAN, 1967, 1969) and of rubidium in
the pyroxene Px-1 (GOLDICH et al., 1967), it seemed that an attempt to measure these elements
by X-ray speotrometry would provide information on the practioal detection limits obtainable
with this technique and illustrate the problems associated with the measurement of trace elements
present in concentrations near or below one part per million. In addition, a comparison co~llrl
be made with results obtained by isotope dilution.

ISOTOPE DII;UTION MEASUREMENTS

Isotopic analyses were made on a modified Metropolitan-Viokers MS-2 mass spectrometer
having magnetic peak switohing and digital output as described by CO~~~PSTONet al. (1965).