Abstract
Fractionations of carbon and oxygen isotopes and magnesium between coexisting dolomite and calcite have been determined for marbles and calcareous schists of a wide variety of metamorphic environments from Vermont and the Grenville Province of Ontario. Concordant equilibrium fractionations are given by 83% of the samples. Calibration of the isotopic thermometers using the Mg-calcite solvus thermometer gave in the temperature range: 650°>T°>100°C
These isotopic fractionation expressions differ significantly from the experimentally derived relations, including the dolomite-Mg-calcite C13 partial exchange experiments of this study.
Temperature ranges obtained for the metamorphic zones of Vermont are: chlorite zone, 210° to 295° C; biotite zone, 255° to 400° C; staurolite-kyanite zone, 110° to 550° C. In amphibolite-facies rocks the quenched partition relations can be complex. The temperature of quench or recrystallization may be as large as 400° C below the inferred metamorphic maximum. Oxygen isotope disequilibrium in high grade rocks, particularly from the Chester dome area, Vermont, is characterized by large negative δO 18D –δO 18Ct values.
The size of the equilibrium exchange system for carbon and oxygen isotopes and magnesium is small, less than a few inches across the inferred relict bedding. This is attributed to the lack of a mobile pore fluid except in systems undergoing decarbonation. C13/C12 ratios in Grenville and Vermont marbles and O18/O16 ratios in Grenville and greenschist-facies Vermont carbonates span the range of ancient limestones. Staurolite-kyanite zone calcareous schists and marbles from the Chester dome area, Vermont are depleted in O18(δO18=12 to 20‰) due to equilibrium or disequilibrium decarbonation and some partial exchange.
Extrapolation of the dolomite-calcite fractionation expressions to 20° C indicates that dolomite is enriched in O18 by about 4.9‰ and in C13 by about 2.4‰.
Similar content being viewed by others
References
Anderson, A. T.: The dimensions of oxygen isotopic equilibrium attainment during prograde metamorphism. J. Geol. 75, 323–332 (1967).
Bain, G. W.: The Vermont marble belt. 16th Int. Geol. Cong Guidebook 1, p. 75–80 (1933).
Berner, R. A.: Dolomitization of the mid-Pacific atolls. Science 147, 1297–1299 (1965).
Bottinga, J.: Calculation of fractionation factors for carbon and oxygen isotopic exchange in the system calcite-carbon dioxide-water. J. Phys. Chem. 72, 800–808 (1968).
Cady, W. M., Albee, A. L., Murphy, J. F.: Bedrock geology of the Lincoln Mountain quadrangle, Vermont. U.S. Geol. Survey Quadrangle Map, GQ-164 (1962).
Clayton, R. N.: Oxygen isotope fractionation in the system calcium carbonate-water. J. Chem. Phys. 30, 1246–1250 (1959).
—: Oxygen isotope fractionation between calcium carbonate and water. J. Chem. Phys. 34, 724 (1961).
—, Jones, B. F., Berner, R. A.: Isotopic studies of dolomite formation under sedimentary conditions. Geochim. Cosmochim. Acta 32, 415–432 (1968).
Craig, H.: The geochemistry of the stable carbon isotopes. Geochim. Cosmochim. Acta 3, 53–92 (1953).
Dale, T. N.: The commercial marbles of western Vermont. U.S. Geol. Surv. Bull. 521, 170 pp. (1912).
Degens, E. T., Epstein, S.: Oxygen and carbon isotope ratios in coexisting calcites and dolomites from recent and ancient sediments. Geochim. Cosmochim. Acta 28, 23–44 (1964).
Doll, C. G.: Geologic map of Vermont. Vermont Geol. Surv. (1961).
Epstein, S., Graf, D. L., Degens, E. T.: Oxygen isotope studies on the origin of dolomites. Isotopic and cosmic chemistry, dedicated to H. C. Urey 70th Birthday (eds. H. Craig, S. L. Miller and G. R. Wasserburg), p. 169–180. Amsterdam: North Holland 1964.
—, Taylor, H. P. Jr.: Variations of O18/O16 in minerals and rocks. Researches in Geochemistry (ed. P. H. Abelson), p. 29–62. New York: John Wiley & Sons 1967.
Evans, A. M.: Geology of Ashby and Denbigh Townships. Ontario Dept. Mines, Geol. Rept. No. 26 (1964).
Fowler, P.: Stratigraphy and structure of the Castleton area, Vermont. Vermont Geol. Surv. Bull. 2, 83 pp. (1950).
French, B. M.: Graphitization of organic material in a progressively metamorphosed Precambrian iron formation. Science 146, 917 (1964).
Friedman, I., Hall, W. E.: Fractionation of O18/O16 between coexisting calcite and dolomite. J. Geol. 71, 238–243 (1963).
Fritz, P.: Oxygen and carbon isotopic composition of carbonates from the Jura of Southern Germany. Can. J. Earth Sci. 4, 1247–1267 (1967).
Garlick, G. D., Epstein, S.: Oxygen isotope ratios in coexisting minerals of regionally metamorphosed rocks. Geochim. Cosmochim. Acta 31, 181–214 (1967).
Goldsmith, J. R.: Exsolution of dolomite from calcite. J. Geol. 68, 103–109 (1960).
- Private communication to H. P. Schwarcz (1962).
—, Graf, D. L., Joensuu, O. I.: The occurrence of magnesian calcites in nature. Geochim. Cosmochim Acta 7, 212–230 (1955).
—, Heard, H. C.: Subsolidus phase relations in the system CaCO3-MgCO3. J. Geol. 69, 45–74 (1961).
Goldsmith, J. R., Newton, R. C.: P-T-X relations in the system CaCO3-MgCO3 at high temperatures and pressures. Am. J. Sci., Schairer Vol. 267-A, 160–190 (1969).
Gross, M. G., Tracey, J. I.: Oxygen and carbon isotopic composition of limestones and dolomites, Bikini and Eniwetock atolls. Science 151, No. 3714, 1082–1084 (1966).
Hewitt, P. C.: The Geology of the Equinox Quadrangle and vicinity, Vermont. Vermont Geol. Surv. Bull. 18, 83 pp. (1961).
James, H. L., Clayton, R. N.: Oxygen isotope fractionation in metamorphosed iron formations of the Lake Superior region and in other iron-rich rocks. Petrologic Studies: A Volume to Honor A. F. Buddington Geol. Soc. Am., 217–239 (1962).
Keith, M. L., Weber, J. N.: Carbon and oxygen isotopic composition of selected limestones and fossils. Geochim. Cosmochim. Acta 28, 1787–1816 (1964).
Lowenstam, H. A., Epstein, S.: On the origin of sedimentary aragonite needles of the Great Bahama Bank. J. Geol. 65, 364–375 (1957).
Lumbers, S. B.: Preliminary report on the relationship of mineral deposits to intrusive rocks and metamorphism in part of the Grenville province of southeastern Ontario. Ontario Dept. Mines. Preliminary Report, 1964-4 (1964).
McCrea, J. M.: On the isotopic chemistry of carbonates and a paleo-temperature scale. J. Chem. Phys. 18, 849–857 (1950).
McNamara, M.: The lower greenschist facies in the Scottish Highlands. Geol. Fören. Förh. 87, 347–389 (1965).
Morey, G. W.: The action of water on calcite, magnesite and dolomite. Am. Mineralogist 47, 1456–1460 (1962).
Newton, R. C.: Kyanite-sillimanite equilibrium at 750°C. Science 151, 1223–1225 (1966).
Northrop, D. A., Clayton, R. N.: Oxygen-isotope fractionations in systems containing dolomite. J. Geol. 74, 174–196 (1966).
O'Neil, J. R., Clayton, R. N.: Oxygen isotope geothermometry. Isotopic and cosmic chemistry, dedicated to H. C. Urey 70th Birthday (eds. H. Craig, S. L. Miller and G. T. Wasserburg), p. 157. Amsterdam: North-Holland 1964.
—, Clayton, R. N. Epstein, S.: Oxygen isotope fractionation in the system dolomite-calcite-CO2. Science 152, 198–201 (1966).
—, Clayton, R. N. Taylor, H. P. Jr.: The oxygen isotope and cation exchange chemistry of feldspars. Am. Mineralogist 52, 1414–1437 (1967).
—, Clayton, R. N. Taylor, H. P., Jr.: Oxygen isotope equilibrium between muscovite and water. J. Geophys. Res. 74, 6012–6022 (1969).
Rosenberg, P. E., Holland, H. D.: Calcite-dolomite-magnesite stability relations in solutions at elevated temperatures. Science 145, 700–701 (1964).
Schwarcz, H. P.: Oxygen and carbon isotopic fractionation between coexisting metamorphic calcite and dolomite. J. Geol. 74, 38–48 (1966).
- Clayton, R. N., Mayeda, T. K.: Oxygen isotope studies of calcareous and pelitic metamorphic rocks of New England, U.S.A. Manuscript in preparation.
Sharma, T., Clayton, R. N.: Measurement of O18/O16 ratios of total oxygen from carbonates. Geochim. Cosmochim. Acta 29, 1347–1354 (1965).
—, Clayton, R. N. Mueller, R. F., Clayton, R. N.: O18/O16 ratios of minerals from the iron formations of Quebec. J. Geol. 73, 664–667 (1965).
Shaw, D. M., Schwarcz, H. P., Sheppard, S. M. F.: The petrology of two zoned scapolite skarns. Can. J. Earth Sci. 2, 577–595 (1965).
Sheppard, S. M. F.: Carbon and oxygen isotope studies in marbles. Ph. D. thesis, McMaster University (1966).
Shieh, Y. N., Taylor, H. P., Jr.: Oxygen and carbon isotope studies of contact metamorphism of carbonate rocks. J. Petrol. 10, 307–301 (1969).
Silver, L. T., Lumbers, S. B.: Geochronologic studies in the Bancroft-Madoc area of the Grenville Province, Ontario, Canada. Geol. Soc. Am. Annual Meeting, Kansas City, 153 (1965).
Skehan, J. W.: The Green Mountain anticlinorium in the vicinity of Wilmington and Woodford, Vermont. Vermont Geol. Surv. Bull. 17, 159 pp. (1961).
Takenouchi, S., Kennedy, G. C.: The binary system H2O-CO2 at high temperatures and pressures. Am. J. Sci. 262, 1055–1074 (1964).
Taylor, H. P., Jr.: Oxygen isotope studies of anorthosites, with special reference to the origin of bodies in the Adirondack Mountains, New York. Origin of Anorthosites, N.Y. State Museum Spec. Publ., in press (1969).
—, Albee, A. L., Epstein, S.: O18/O16 Ratios of coexisting minerals in three assemblages of kyanite-zone pelitic schist. J. Geol. 71, 513–522 (1963).
—, Coleman, R. G.: O18/O16 ratios of coexisting minerals in glaucophane-bearing metamorphio rocks. Bull Geol. Soc. Am. 79, 1727–1756 (1968).
—, Epstein, S.: Comparison of oxygen isotope analyses of tektites, soils, and impactite glasses. Isotopic and Cosmic Chemistry (ed. Craig, Miller and Wasserburg), p. 181–199. Amsterdam: North Holland 1964.
Thompson, J. B.: Southern Vermont; Guidebook for field trips in New England. Geol. Soc. Am., 65th annual meeting, 14 (1952).
- Stratigraphy and structure in the Vermont Valley and the eastern Taconics between Clarendon and Dorset. New England Intercoll. Geol. Conf., Guidebook, 51st Annual Meeting, p. 71–87 (1959).
Tuttle, O. F.: Two pressure vessels for silicate-water studies. Bull. Geol. Soc. Am. 60, 1727–1729 (1949).
Weber, J. N.: Oxygen isotope fractionations between coexisting calcite and dolomite. Science 145, 1303–1305 (1964).
—: Factors affecting the carbon and oxygen isotopic composition of marine carbonate sediments, Part I, Bermuda. Am. J. Sci. 265, 586–608 (1967).
Wynne-Edwards, H. R.: Westport map area, Ontario. Geol. Survey Canada, Map 28-1959 (1959).
Zen, E.: Metamorphism of Lower Paleozoic rocks in the vicinity of the Taconic Range in west-central Vermont. Am. Mineralogist 45, 129–175 (1960).
Author information
Authors and Affiliations
Rights and permissions
About this article
Cite this article
Sheppard, S.M.F., Schwarcz, H.P. Fractionation of carbon and oxygen isotopes and magnesium between coexisting metamorphic calcite and dolomite. Contr. Mineral. and Petrol. 26, 161–198 (1970). https://doi.org/10.1007/BF00373200
Received:
Issue Date:
DOI: https://doi.org/10.1007/BF00373200