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Carbon isotope ratios and nitrogen abundances in relation to cathodoluminescence characteristics for some diamonds from the Kaapvaal Province, S. Africa

Published online by Cambridge University Press:  05 July 2018

B. Harte ,
I. C. W. Fitzsimons ,
J. W. Harris  and
M. L. Otter
B. Harte
Affiliation:
Department of Geology and Geophysics, University of Edinburgh, King's Buildings, Edinburgh EH9 3JW, UK
I. C. W. Fitzsimons
Affiliation:
Department of Geology and Geophysics, University of Edinburgh, King's Buildings, Edinburgh EH9 3JW, UK
J. W. Harris
Affiliation:
Division of Earth Sciences, University of Glasgow, Lilybank Gardens, Glasgow G12 8QQ, UK
M. L. Otter
Affiliation:
Department of Geological Sciences, University of Cape Town, Rondebosch 7700, South Africa
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Abstract

Secondary ion mass spectrometry (SIMS) techniques have been used to study the variation of C isotope ratio and N abundance within selected diamonds in relation to their crystal growth zones. The growth zones are seen in cathodoluminescence (CL), and include both octahedral and cuboid zones within typical diamonds of external octahedral morphology. Compositions were determined by use of a primary 133Cs+ ion beam and measurement of 12C−, 13C, and 12C14N− secondary ions at high mass resolution on a Cameca ims-4f ion microprobe at Edinburgh University.

In each of the diamonds, different growth zones have marked differences in N abundance, which are as great as 0–1400 ppm within one diamond. Changes of several hundred ppm N are common across both octahedral and cuboid growth zones, and appear sharp and abrupt at the boundaries of the growth zones. In general for the common blue CL, luminescence increases with N abundance. The changes in N abundance across fine scale (∼100 µm) growth zones show that the total N contents determined by IR spectroscopy may show great variations of abundance. In contrast, within detection limits, δ13C appears constant across many growth zone boundaries. Thus the factors controlling uptake of N from the fluid/melt reservoir in which natural diamonds grow often do not influence δ13C. No evidence of progressive variation or fractionation of C isotopes during growth was found.

Some original variation in C isotope composition may have been eliminated by diffusion of C atoms subsequent to growth, because of the storage of natural diamonds over millions of years in the Earth's mantle at temperatures of 950–1250°C. Such atomic mobility does not homogenize N distribution because of the proven tendency of N to form aggregates of atoms. A survey of experimental estimates of single atom (C) diffusion parameters, suggests that diffusion distances of ∼100 µm are likely at high temperatures (∼1100°C) over long time periods (∼1.0 Ga). Therefore, with refinement of the diffusion parameters and measurements, the extent of C isotope homogenization in natural diamonds, as well as N aggregation state, might provide quantitative evidence of their time-temperature history under mantle conditions.

Keywords

diamondscathodoluminescencecrystal growth zonesnitrogen abundancescarbon isotopesdiffusion
Type
Research Article
Information
Mineralogical Magazine , Volume 63 , Issue 6 , December 1999 , pp. 829 - 856
Copyright
Copyright © The Mineralogical Society of Great Britain and Ireland 1999

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Footnotes

*

Present address: School of Applied Geology, Curtin University of Technology, GPO Box U1987, Perth 6001, Australia

References

Boyd, F.R. and Gurney, J.J. (1986) Diamonds and the African lithosphere. Science, 232, 472–7.CrossRefGoogle ScholarPubMed
Boyd, S.R. and Pillinger, C.T. (1994) A preliminary study of 15N/14N in octahedral growth form diamonds. Chem. Geol., 116, 43–59.CrossRefGoogle Scholar
Boyd, S.R., Pillinger, C.T., Milledge, H.J., Mendelssohn, M.J. and Seal, M. (1992) C and N isotopic composition and the infrared absorption spectra of coated diamonds: evidence for the regional uniformity of CO2-H2O fluids in lithospheric mantle. Earth Planet. Sci. Lett., 109, 633–44.CrossRefGoogle Scholar
Boyd, S.R., Pineau, F. and Javoy, M. (1994) Modelling the growth of natural diamonds. Chem. Geol., 116, 29–42.CrossRefGoogle Scholar
Burgess, R., Turner, G., Laurenzi, M., and Harris, J.W. (1989) 40Ar-39Ar laser probe dating of individual clinoproxene inclusions in premier eclogitic diamonds. Earth Planet. Sci. Lett., 94, 22–8.CrossRefGoogle Scholar
Bulanova, G.P. (1995) Origin of Diamond. J. Geochem. Expl., 53, 1–23.CrossRefGoogle Scholar
Burns, R.C. and Davies, G.J. (1992) Growth of synthetic diamond. In The properties of natural and synthetic diamond (Field, J.E., ed.). Academic Press, London, pp. 395–422.Google Scholar
Burns, R.C., Cvetkovic, V., Dodge, C.N., Evans, D.J.F., Rooney, M.L.T., Spear, P.M. and Welbourn, C.M. (1990) Growth sector dependence of optical features in large synthetic diamonds. J. Cryst. Growth, 104, 257–79.CrossRefGoogle Scholar
Chrenko, R.M., Tuft, R.E. and Strong, H.M. (1977) Transformation of the state of nitrogen in diamond. Nature, 270, 141–4.CrossRefGoogle Scholar
Clark, C.D., Collins, A.T. and Woods, G.S. (1992) Absorption and luminescence spectroscopy. In The properties of natural and synthetic diamond (Field, J.E., ed.). Academic Press, London, pp. 35–79.Google Scholar
Davies, G. (1974) Vibronic spectra in diamond. J. Physics C: Solid State Physics, 7, 3797–809.CrossRefGoogle Scholar
Deines, P. (1980) The carbon isotopic composition of diamonds: relationship to diamond shape, color, occurrence and vapor composition. Geochim. Cosmochim. Acta, 44, 943–61.CrossRefGoogle Scholar
Deines, P. (1996) The role of mantle fluids in the growth of diamonds. In Advanced materials ‘96. Proceedings of 3rd NIRIM Int. Symp. on Advanced Materials (ISAM `96). NIRIM, Tsukuba, pp. 61–4.Google Scholar
Deines, P., Harris, J.W. and Gurney, J.J. (1991) The carbon isotopic composition and nitrogen content of lithospheric and asthenospheric diamonds from the Jagersfontein and Koffiefontein kimberlite, South Africa. Geochim. Cosmochim. Acta, 55, 2615–25.CrossRefGoogle Scholar
Deines, P., Harris, J.W. and Gurney, J.J. (1993) Depth- related carbon isotope and nitrogen concentration variability in the mantle below the Orapa kimberlite, Botswana, Africa. Geochim. Cosmochim. Acta, 57, 2781–97.CrossRefGoogle Scholar
Dodson, M.H. (1986) Closure profiles in cooling systems. Mat. Sci. Forum, 7, 145–54.CrossRefGoogle Scholar
Eiler, J.M., Valley, J.W., Graham, C.M. and Baumgartner, L.P. (1995) Ion microprobe evidence for the mechanisms of stable isotope retrogression in high-grade metamorphic rocks. Contrib. Mineral. Petrol., 118, 365–78.CrossRefGoogle Scholar
Evans, T. (1992) Aggregation of nitrogen in diamond. In The properties of natural and synthetic diamond (Field, J.E., ed.). Academic Press, London, pp. 259–90.Google Scholar
Evans, T. and Harris, J.W. (1989) Nitrogen aggregation, inclusion equilibration temperatures and the age of diamonds. In: Kimberlites and related rocks, vol. 2, The mantle/crustal setting diamonds and diamond exploration (Ross, J., ed.). Geologic Society of Australia Special Publication, 14, Blackwell Scientific, Melbourne, pp. 1001–6.Google Scholar
Field, J.E. (1992) The properties of natural and synthetic diamond. Academic Press, London, 710 pp.Google Scholar
Fitzsimons, I.C.W., Harte, B., Chinn, I.L., Gurney, J.J. and Taylor, W.R. (1999) Extreme chemical variation in complex diamonds from George Creek, Colorado: a SIMS study of nitrogen abundance and carbon isotope compositon. Mineral. Mag., 63, 857–78.CrossRefGoogle Scholar
Fitzsimons, I.C.W., Harte, B. and Clark, R.M. (2000) SIMS stable isotope measurement: counting statistics and analytical precision. Mineral. Mag., in press.CrossRefGoogle Scholar
Galimov, E.M. (1991) Isotope fractionation related to kimberlite magmatism and diamond formation. Geochim. Cosmochim. Acta, 55, 1697–708.CrossRefGoogle Scholar
Gurney, J.J. (1989) Diamonds. In: Kimberlites and related rocks, vol. 2, The mantle/crustal setting diamonds and diamond exploration (Ross, J., ed.). Geologic Society of Australia Special Publication, 14, Blackwell Scientific, Melbourne, pp. 935–65.Google Scholar
Haggerty, S.E. (1986) Diamond genesis in a multiply-constrained model. Nature, 320, 34–8.CrossRefGoogle Scholar
Harris, J.W. (1987) Recent physical, chemical, and isotopic research of diamond. In Mantle xenoliths (Nixon, P.H., ed.). John Wiley & Sons, Chichester, pp. 477–500.Google Scholar
Harris, J.W. (1992) Diamond geology. In The properties of natural and synthetic diamond (Field, J.E., ed.). Academic Press, London, pp. 345–93.Google Scholar
Harris, J.W. and Gurney, J.J. (1979) Inclusions in diamond. In: The properties of diamond (Field, J.E., ed.). Academic Press, London, pp. 555–91.Google Scholar
Harris, J.W., Hawthorne, J.B., Oosterveld, M.M. and Wehmeyer, E. (1975) A classification scheme for diamond and a comparative study of South African diamond characteristics. In: Physics and Chemistry of the Earth, 9 (Ahrens, L.H. et al., eds). Pergamon, Oxford, pp. 765–83.CrossRefGoogle Scholar
Harte, B. and Otter, M. (1992) Carbon isotope measurements on diamonds. Chem. Geol., 101, 177–83.Google Scholar
Hoppe, P., Amari, S., Zinner, E. and Lewis, R.S. (1995) Isotopic compositions of C, N, O, Mg, and Si, trace element abundances, and morphologies of single circumstellar graphite grains in 4 density fractions from the Murchison meteorite. Geochim. Cosmochim. Acta, 59, 4029–56.CrossRefGoogle Scholar
Javoy, M., Pineau, F. and Delorme, H. (1986) Carbon and nitrogen isotopes in the mantle. Chem. Geol., 57, 41–62.CrossRefGoogle Scholar
Kanda, H. (1996) Temperature effect on impurities in high pressure synthetic diamonds. In Advanced materials ‘96. Proceedings of 3rd NIRIM Int. Symp. Advanced Materials (ISAM ‘96). NIRIM, Tsukuba, pp. 113–8.Google Scholar
Kanda, H., Ohsawa, T. and Yamaoka, S. (1990) Formation of nitrogen pairs in synthetic diamond during growth. In Science and technology of new diamond (Saito, S. et al., eds). Terra Scientific Publishing, Tokyo, pp. 339–44.Google Scholar
Kirkley, M.B., Gurney, J.J., Otter, M.L., Hill, S.J. and Daniel, L.R. (1991) The application of C isotope measurements to the identification of the sources of C in diamonds: a review. Appl. Geochem., 6, 477–94.CrossRefGoogle Scholar
Lang, A.R. (1974 a) On the growth–sectorial dependence of defects in natural diamonds. Proc. Roy. Soc. Lond., A340, 233–48.Google Scholar
Lang, A.R. (1974 b) Space-filling by branching columnar single-crystal growth: an example from crystallisation of diamond. J. Cryst. Growth, 23, 151–3.CrossRefGoogle Scholar
Lang, A.R., Moore, M. and Walmsley, J.C. (1992) Diffraction and imaging studies of diamond. In: The properties of natural and synthetic diamond (Field, J.E., ed.). Academic Press, London, pp. 215–58.Google Scholar
Mainwood, A. (1994) Nitrogen and nitrogen-vacancy complexes and their formation in diamond. Phys. Rev., B49, 7934–40.CrossRefGoogle Scholar
Marfunin, A.S. (1979) Spectroscopy, Luminescence, and Radiation Centers in Minerals. Translated from the Russian publication by Schiffer, V.V.. Springer Verlag, Berlin.CrossRefGoogle Scholar
Marshall, D.J. (1988) Cathodoluminescence of Geologic Materials. Unwin Hyman, London.Google Scholar
McKeegan, K.D., Walker, R.M. and Zinner, E. (1985) Ion microprobe isotopic measurements of individual interplanetary dust particles. Geochim. Cosmochim. Acta, 49, 1971–87.CrossRefGoogle Scholar
Meyer, H.O.A.(1987) Inclusions in diamond. In Mantle Xenoliths (Nixon, P.H., ed.). J. Wiley & Sons, Chichester, pp. 501–22.Google Scholar
Narducci, D. and Cuomo, J.J. (1990) Boron diffusivity in nonimplanted diamond single crystals measured by impedance spectroscopy. J. Appl. Phys., 68, 1184–6.CrossRefGoogle Scholar
Poferl, D.J., Gardner, N.C. and Angus, J.C. (1973) Growth of boron-doped diamond seed crystals by vapour deposition. J. Appl. Phys., 44, 1428–34.CrossRefGoogle Scholar
Richardson, S.H. and Harris, J.W. (1997) Antiquity of peridotitic diamonds from the Siberian craton. Earth Planet. Sci. Lett. 151, 271–7.CrossRefGoogle Scholar
Richardson, S.H., Gurney, J.J., Erlank, A.J. and Harris, J.W. (1984) Origin of diamonds in old enriched mantle. Nature, 310, 198–202.CrossRefGoogle Scholar
Richardson, S.H., Harris, J.W. and Gurney, J.J. (1993) Three generations of diamonds from old continental mantle. Nature, 366, 256–8.CrossRefGoogle Scholar
Rickard, R.S., Harris, J.W., Gurney, J.J. and Cardoso, P. (1989) Mineral inclusions in diamonds from the koffiefontein mine. In Kimberlites and Related Rocks, Vol. 2, the Mantle/Crustal Setting Diamonds and Diamond Exploration (Ross, J., ed.). Geologic Society of Australia Special Publication, 14, Blackwell Scientific, Melbourne, pp. 1054–62.Google Scholar
Robinson, D.N. (1978) The characteristics of natural diamond and their interpretation. Mineral. Sci. Eng., 10, 55–72.Google Scholar
Ryan, B.F. and Joiner, B.L. (1994) Minitab Handbook. Duxbury Press, Belmont.Google Scholar
Sato, Y. and Kamo, M. (1992) Synthesis of diamond from the vapour phase. The Properties of Natural and Synthetic Diamond (Field, J.E., ed.). Academic Press, London, pp. 423–69.Google Scholar
Satoh, S., Sumiya, H., Tsuji, K. and Yazu, S. (1990) Difference in nitrogen concentration and aggregation among (111) and (100) growth sectors of large synthetic diamonds. In Science and technology of new diamond (Saito, S. et al., eds). Terra Scientific Publishing, Tokyo, pp. 351–5.Google Scholar
Slodzian, G. (1980) Microanalyzers using secondary ion emission. Adv. Electronics Electron Phys. Suppl., 13B, 1–44.Google Scholar
Slodzian, G., Wu, T.D., Dennebouy, R., Chaintreau, M., and Rasser, B. (1997) On precision and reproduci- bility of in situ isotopic measurements. In Secondary Ion Mass Spectrometry: SIMS X (Benninghoven, A., Hagenhoff, B. and Werner, H.W., eds). John Wiley & Sons, Chichester, pp. 31–38.Google Scholar
Smith, C.B., Gurney, J.J., Harris, J.W., Otter, M.L., Kirkley, M.B. and Jagoutz, E. (1991) Neodymium and strontium isotope systematics of eclogite and websterite paragenesis inclusions from single dia- monds, Finsch and Kimberley Pool, RSA. Geochim. Cosmochim. Acta, 55, 2579–90.CrossRefGoogle Scholar
Stoneham, A.M. (1992) Diamond: recent advances in theory. In: The Properties of Natural and Synthetic Diamond (Field, J.E., ed.). Academic Press, London, pp. 3–34.Google Scholar
Sunagawa, I. (1984) Morphology of natural and synthetic diamond crystals. In Materials science of the Earth's interior (Sunagawa, I., ed.). Terra Scientific Publishing, Tokyo, pp. 303–30.Google Scholar
Storms, H.A., Brown, K.F. and Stein, J.D. (1977) Evaluation of a cesium positive ion source for secondary ion mass spectrometry. Anal. Chem., 49, 2023–30.CrossRefGoogle Scholar
Swalin, R.A. (1961) Theoretical calculations of the enthalpies and entropies of diffusion and vacancy formation in semiconductors. J. Phys. Chem. Solids, 18, 290–96.CrossRefGoogle Scholar
Swart, P.K., Pillinger, C.T., Milledge, H.J. and Seal, M. (1983) Carbon isotopic variation within individual diamonds. Nature, 303, 793–5.CrossRefGoogle Scholar
Taylor, W.R., Jaques, A.L. and Ridd, M. (1990) Nitrogen-defect aggregation characteristics of some Australasian diamonds: time-temperature constraints on the source regions of pipe and alluvial diamonds. Amer. Mineral., 75, 1290–310.Google Scholar
Taylor, W.R., Canil, D. and Milledge, H.J. (1996) Kinetics of Ib to IaA nitrogen aggregation in diamond. Geochim. Cosmochim. Acta, 60, 4725–33.CrossRefGoogle Scholar
Valley, J.W., Graham, C.M., Harte, B., Eiler, J.M. and Kinny, P.D. (1991) Ion microprobe analysis of oxygen, carbon and hydrogen isotope ratios. In Application of microanalytical techniques to understanding mineralizing processes (McKibben, M.A. and Shanks, W.C., eds). Reviews in Economic Geology, 7, pp. 73–98.Google Scholar
Vavilov, V.S. (1978) Ion implantation into diamond. Radiat. Eff., 37, 229–36.CrossRefGoogle Scholar
Wentorf, R.H. Jr. and Bovenkerk, H.P. (1962) Preparation of semiconducting diamonds. J. Chem. Phys., 36, 1987–90.CrossRefGoogle Scholar
Wilding, M.C. (1990) A study of diamonds with syngenetic inclusions. Unpubl. Ph.D. thesis, Univ. Edinburgh, 280 pp.Google Scholar
Wilding, M.C., Harte, B., Fallick, A.E. and Harris, J.W. (1994) Inclusion chemistry, carbon isotopes and nitrogen distribution in diamonds from the Bultfontein mine, South Africa. In: Proc. 5th Int. Kimberlite Conference (Meyer, H.O.A. and Leonardos, O.H., eds). CPRM Special Publication 1/B Jan/ 94, Brasilia, pp. 116–26.Google Scholar
Zinner, E., Ming, T. and Anders, E. (1989) Interstellar SiC in the Murchison and Murray meteorites: isotopic composition of Ne, Xe, Si, C and N. Geochim. Cosmochim. Acta, 53, 3273–90.CrossRefGoogle Scholar