Skip to main content
Log in

In situ cryogenic Raman spectroscopic studies on the synthetic fluid inclusions in the systems H2O and NaCl-H2O

  • Articles
  • Published:
Chinese Science Bulletin

Abstract

Salt-hydrates have diagnostic cryogenic Raman spectra, which can reflect the composition of the parent solutions. As analogue to the natural fluid inclusions, the synthetic inclusions can be used to validate numerous assumptions related to fluid inclusion research. They can also be used to test the feasibility of application of laser Raman spectroscopy to individual fluid inclusion analysis. Using the technique proposed by Sterner and Bodnar(1984), synthetic inclusions of the systems H2O and NaCl-H2O (with NaCl as 5.12 wt%, 9.06 wt%, 16.6 wt% and 25 wt%) were formed under the pressures from 50Mpa to 100Mpa and at the temperatures from 500°C? to 600°C. In situ cryogenic Raman spectra were collected at about −180°C by combined use of freezing-heating stage and Laser Raman Microscopy. It is shown that hydrohalite (NaCl·2H2O), the salt-hydrate of NaCl in the fluid inclusions has the specific Raman spectrum and can be used as the standard to verify the existence of NaCl in the aqueous inclusions. The crystalline ice other than amorphous ice (glasses) formed from the aqueous phase whthin the synthetic inclusions during the initial freezing, but hydrohalite did not form. Subsequent warming of these inclusions induced a phase change, typically between approximately −40 and −22°C, that represents the hydrohalite crystallization event but not a eutectic melting event. So, for fluid inclusions in the system NaCl-H2O, interpretation of phase behavior below the eutectic temperature (−20.8?) should be made with caution. The ratios of the relative intensity and the area of Raman spectra between 3423 cm−1 peak of hydrohalite and 3098 cm−1 peak of ice show positive correlations to the salinities in aqueous inclusions, which can be used to determine the salinity of NaCl-H2O system inclusions.

This is a preview of subscription content, log in via an institution to check access.

Access this article

Price excludes VAT (USA)
Tax calculation will be finalised during checkout.

Instant access to the full article PDF.

Similar content being viewed by others

References

  1. Roedder, E., Composition of fluid inclusions, U. S. Geol. Survey Prof. Paper, 1972, 440JJ: 164.

    Google Scholar 

  2. Roedder, E., Fluid inclusions, Mineral. Soc. Amer., Reviews in Mineralogy, 1984, 12: 644.

    Google Scholar 

  3. Roedder, E., Ingram, B., Hall, W. E., Studies of fluid inclusions.III: Extraction and quantitative analysis of inclusion in the milligram range, Econ. Geol., 1963, 58:343–374.

    Google Scholar 

  4. Crawford, M. L., Phase equilibria in aqueous fluid inclusions, in Fluid Inclusions: Applications to Petrology (eds. Hollister, L. S., Crawford, M. L.), Min. Assoc. Canada Short Course Handbook, Calgary: Albeta, 1981, 6: 157-181.

  5. Goldstein, R. H., Reynolds, T. J., Systematics of fluid inclusions in diagenetic minerals, in S.E.P.M. Short Course, Tulsa: Oklahoma, 1994, 31: 1-199.

  6. Dubessy, J., Audeoud, D., Wilkins, R., Kosztolanyi, C., The use of the Raman microscopy mole in the determination of the electrolytes dissolved in the aqueous phase of fluid inclusion, Chemical Geology, 1982, 37: 137–150.

    Article  Google Scholar 

  7. Samson, I. M., Walker, R. T., Cryogenic Raman spectroscopic studies in the system NaCl-CaCl2-H2O and implications for low-temperature phase behavior in aqueous fluid inclusion, The Canadian Mineralogist, 2000, 38: 35–43.

    Google Scholar 

  8. Ni P., Rao B., Ding J. Y., Zhang L. S., Studies on the synthetic fluid inclusions and their application to laser Raman spectrum analysis field, Acta Petrologica Sinica, 2003, 19(2): 319–326.

    Google Scholar 

  9. Sterner, S. M., Bodnar, R. J., Synthetic fluid inclusions in Natural Quartz I. Compositional types synthesized and applications to experimental geochemistry, Geochim. Cosmochim. Acta, 1984, 48: 2659–2668.

    Article  Google Scholar 

  10. Bodnar, R. J., Sterner, S. M., Application of synthetic fluid inclusions to phase equilibria studies[abs.], EOS, 1984, 65: 292.

    Google Scholar 

  11. Bodnar, R. J., Burnham, C. W., Sterner, S. M., Synthetic fluid inclusions in Natural Quartz III. Determination of phase equilibrium properties in the system H2O-NaCl to 1000 and 1500 bars, Geochim. Cosmochim. Acta, 1985, 49: 1861–1873.

    Google Scholar 

  12. Zhang, Y. G., Frantz, J. D., Determination of the homogenization temperatures and density of supercritical fluids in the system NaCl-KCl-CaCl2-H2O using synthetic fluid inclusions, Chemical Geology, 1987, 64: 335–350.

    Article  Google Scholar 

  13. Lamb, W. M., Popp, R. K., Boockoff, L. A., The determination of phase relations in the CH4-H2O-NaCl system at 1 kbar, 400 to 800°C using synthetic fluid inclusions?, Geochim. Cosmochim. Acta, 1996, 60: 1885–1897.

    Article  Google Scholar 

  14. Bodnar, R. J., Revised equation and table for determining the freezing point depression of H2O-NaCl solutions, Geochim. Cos-mochim. Acta, 1993, 57: 683–684.

    Google Scholar 

  15. Handa, Y. P., Mishima, O., Whalley, E., High-density amorphous ice. Thermal properties, J. Chem. Phys., 1986, 84: 2766–2770.

    Google Scholar 

  16. Tulk, C. A., Klug, D. G., Barnderhorst, R. et al., Hydrogen bonding in glassy liquid water from Raman spectroscopic studies, J. Chem. Phys., 1998, 109: 8478–8484.

    Article  Google Scholar 

  17. Mcmillan, J. A., Los, S. C., Vitreous ice: irreversible transformations during warm-up, Nature, 1965, 206: 806–807.

    Google Scholar 

  18. Hallbrucker, A., Mayer, E., Joharl, G. P., Glass transition in pressure-amorphized hexagonal ice. A comparison with amorphous forms made from the vapor and liquid, J. Phys. Chem., 1989, 93: 7751–7752.

    Google Scholar 

  19. Klug, D. D., Mishima, O., Whalley, E., High-density amorphous ice IV.Raman spectrum of the uncoupled O-H and O-D oscillators, J. Chem. Phys., 1987, 86: 5323–5328.

    Article  Google Scholar 

  20. Bruggelle, P., Mayer, E., Complete vitrification in pure liquid water and dilute aqueous solutions, Nature, 1980, 288: 569–571.

    Google Scholar 

  21. Mayer, E., New method for vitrifying water and other liquids by rapid cooling of their aerosols, J. Appl. Phys., 1985, 58: 663–667.

    Article  Google Scholar 

  22. Burton, E. F., Oliver, W. F., The crystal structure of ice at low temperatures, Proc. R. Soc., 1935, A153: 166–172.

    Google Scholar 

  23. Mishima, O., Calvert, L. D., Whalley, E., “Melting ice” I at 77K and 10 kbar: a new method of making amorphous solids, Nature, 1984, 310: 393–395.

    Article  Google Scholar 

  24. Walrafen, G. E., Raman spectral studies of water structure, J. Chem. Phys, 1964, 40: 3249–3256.

    Google Scholar 

  25. Walrafen, G. E., Raman and infrared spectral investigations of water structure, in Water, A Comprehensive Treatise. 1. The physics and physical chemistry of water (eds. Franks, F.), New York: Plenum Press, 1972, 151–214.

    Google Scholar 

  26. Walrafen, G. E., Raman spectral studies of the effects of electrolytes on water, J Chem. Phys., 1962, 36: 1035–1042.

    Google Scholar 

  27. Mernagh, T. P., Wilde, A. R., The use of the laser Raman microprobe for the determination of salinity in fluid inclusions, Geochim. Acta, 1989, 53: 765–771.

    Google Scholar 

  28. Davis, D. W., Lowenstern, T. K., Spencer, R. J., Melting behavior of fluid inclusions in laboratory-grown halite crystals in the systems NaCl-H2O. NaCl-KCl-H2O, NaCl-MgCl2, NaCl-CaCl2-H2O, Geochim. Cosmochim. Acta, 1990, 54: 591–601.

    Article  Google Scholar 

  29. Vanko, D. A., Bodnar, R. J., Sterner, S. M., Synthetic fluid inclusions. VIII. Vapor-saturated halite solubility in part of the system NaCl-CaCl2-H2O, with application to fluid inclusions from oceanic hydrothermal systems, Geochim. Cosmochim. Acta, 1988, 52: 2451–2456.

    Article  Google Scholar 

  30. Ding, J. Y., Ni, P., Rao, B. et al., Evaluation of the laser Raman microprobe method for the determination of salinity in a single fluid inclusion by using synthetic fluid inclusions, Geological Review, 2004, 50(2): 203–209.

    Google Scholar 

Download references

Author information

Authors and Affiliations

Authors

About this article

Cite this article

Ni, P., Ding, J. & Rao, B. In situ cryogenic Raman spectroscopic studies on the synthetic fluid inclusions in the systems H2O and NaCl-H2O. CHINESE SCI BULL 51, 108–114 (2006). https://doi.org/10.1007/s11434-004-0256-5

Download citation

  • Received:

  • Accepted:

  • Issue Date:

  • DOI: https://doi.org/10.1007/s11434-004-0256-5

Keywords

Navigation