Skip to content
Licensed Unlicensed Requires Authentication Published by De Gruyter February 9, 2017

Determination of pressure in aqueo-carbonic fluid inclusions at high temperatures from measured Raman frequency shifts of CO2

  • Xueyin Yuan , Robert A. Mayanovic , Haifei Zheng and Qiang Sun EMAIL logo
From the journal American Mineralogist

Abstract

Due to the presence of additional volatiles and/or electrolytes in CO2-H2O fluids, the total pressure of many natural aqueo-carbonic fluid inclusions at high temperatures as determined using microthermometry is usually made with considerable uncertainty. In this paper, we present the results of our high P-T in situ Raman scattering study of high-density aqueo-carbonic fluids, with and without a small amount of CH4 and NaCl, whose objective is to derive a new method for pressure determination in aqueo-carbonic fluid inclusions at high temperatures. The measurement of the Fermi dyad bands at temperatures up to 400°C and pressures up to 1200 MPa is described. The manner in which the frequency shifts and intensity of Raman bands are governed by pressure, temperature, presence of CH4 in carbonic and NaCl in aqueous fluids is discussed. From the monotonic dependence of the frequency shifts of the lower Fermi dyad band vand the Fermi resonant splitting D (D = v+– v) with pressure and temperature, the pressure (in MPa) in aqueo-carbonic fluid inclusions at elevated temperatures can be determined directly by using the following two polynomial equations:

P(MPa)=16+1.232×T53.72×(Δν)1.83×103×T2+24.46×(Δν)20.292×T×(Δν),P(MPa)=26+1.501×T+193.24×(ΔD)1.61×103×T2+5.436×(ΔD)2+0.158×T×(ΔD),

whereT is in °C, Δνand ΔD represent frequency shifts (in cm−1) of the lower band and the resonant splitting relative to the reference values measured at 23 °C and 6 MPa, respectively. Based on the attainable accuracy of the fitted peak positions and the results from fitting of Raman frequency shifts’ dependence with pressure and temperature, the uncertainty in pressure determination is about 50 MPa for pressures determined from ν– and 40 MPa from that determined from D.

Acknowledgments

This work is supported by National Natural Science Foundation of China (No. 41373057) and by the China Scholarship Council (No. 201406010059). We are sincerely grateful to Robert J. Bodnar and an anonymous reviewer for their critical comments and valuable suggestions.

References cited

Akinfiev, N.N., and Diamond, L.W. (2010) Thermodynamic model of aqueous CO2–H2O–NaCl solutions from –22 to 100 °C and from 0.1 to 100 MPa. Fluid Phase Equilibria, 295, 104–124.10.1016/j.fluid.2010.04.007Search in Google Scholar

Aranovich, L.Y., Zakirov, I., Sretenskaya, N., and Gerya, T. (2010) Ternary system H2O–CO2–NaCl at high T-P parameters: An empirical mixing model. Geochemistry International, 48(5), 446–455.10.1134/S0016702910050022Search in Google Scholar

Azbej, T., Severs, M.J., Rusk, B.G., and Bodnar, R.J. (2007) In situ quantitative analysis of individual H2O–CO2 fluid inclusions by laser Raman spectroscopy. Chemical Geology, 237(3–4), 255–263.10.1016/j.chemgeo.2006.06.025Search in Google Scholar

Bakker, R.J., and Diamond, L.W. (2000) Determination of the composition and molar volume of H2O–CO2 fluid inclusions by microthermometry. Geochimica et Cosmochimica Acta, 64(10), 1753–1764.10.1016/S0016-7037(99)00334-8Search in Google Scholar

Bassett, W., Shen, A., Bucknum, M., and Chou, I.M. (1993) A new diamond anvil cell for hydrothermal studies to 2.5 GPa and from −190 to 1200 °C. Review of Scientific Instruments, 64(8), 2340–2345.10.1063/1.1143931Search in Google Scholar

Berkesi, M., Hidas, K., Guzmics, T., Dubessy, J., Bodnar, R.J., Szabó, C., Vajna, B., and Tsunogae, T. (2009) Detection of small amounts of H2O in CO2–rich fluid inclusions using Raman spectroscopy. Journal of Raman Spectroscopy, 40(11), 1461–1463.10.1002/jrs.2440Search in Google Scholar

Bersani, D., Salvioli-Mariani, E., Mattioli, M., Menichetti, M., and Lottici, P.P. (2009) Raman and micro-thermometric investigation of the fluid inclusions in quartz in a gold-rich formation from Lepaguare mining district (Honduras, Central America). Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy, 73(3), 443–449.10.1016/j.saa.2008.10.046Search in Google Scholar

Bodnar, R.J. (2003) Reequilibration of fluid inclusions. In A.A. Samson and D. Marshall, Eds., Fluid Inclusions: Analysis and interpretation, 32, p. 213–230. Mineralogical Association of Canada.Search in Google Scholar

Bodnar, R.J., Binns, P.R., and Hall, D.L. (1989) Synthetic fluid inclusions-VI. Quantitative evaluation of the decrepitation behaviour of fluid inclusions in quartz at one atmosphere confining pressure. Journal of Metamorphic Geology, 7(2), 229–242.10.1111/j.1525-1314.1989.tb00586.xSearch in Google Scholar

Burke, E.A.J. (2001) Raman microspectrometry of fluid inclusions. Lithos, 55(1–4), 139–158.10.1016/S0024-4937(00)00043-8Search in Google Scholar

Chen, Y., Zhou, Y., and Ni, P. (2006) A new method for measurement of internal pressure of inclusions: CO2-Raman spectrometry. Rock and Mineral Analysis, 25(3), 211–214.Search in Google Scholar

Chi, G., Dubé, B., Williamson, K., and Williams-Jones, A. (2006) Formation of the Campbell-Red Lake gold deposit by H2O-poor, CO2-dominated fluids. Mineralium Deposita, 40(6-7), 726–741.10.1007/s00126-005-0029-3Search in Google Scholar

Darling, R.S., and Bassett, W.A. (2002) Analysis of natural H2O+CO2+NaCl fluid inclusions in the hydrothermal diamond anvil cell. American Mineralogist, 87, 69–78.10.2138/am-2002-0108Search in Google Scholar

Diamond, L.W. (1996) Isochoric paths in immiscible fluids and the interpretation of multicomponent fluid inclusions. Geochimica et Cosmochimica Acta, 60(20), 3825–3834.10.1016/0016-7037(96)00200-1Search in Google Scholar

–––(2001) Review of the systematics of CO2–H2O fluid inclusions. Lithos, 55(1–4), 69–9910.1016/S0024-4937(00)00039-6Search in Google Scholar

Fall, A., Tattitch, B., and Bodnar, R.J. (2011) Combined microthermometric and Raman spectroscopic technique to determine the salinity of H2O–CO2–NaCl fluid inclusions based on clathrate melting. Geochimica et Cosmochimica Acta, 75(4), 951–964.10.1016/j.gca.2010.11.021Search in Google Scholar

Garrabos, Y., Tufeu, R., Le Neindre, B., Zalczer, G., and Beysens, D. (1980) Rayleigh and Raman scattering near the critical point of carbon dioxide. The Journal of Chemical Physics, 72(8), 4637–4651.10.1063/1.439706Search in Google Scholar

Garrabos, Y., Echargui, M.A., and Marsault-Herail, F. (1989) Comparison between the density effects on the levels of the Raman spectra of the Fermi resonance doublet of the 12C16O213C16O2 molecules. The Journal of Chemical Physics, 91, 5869–5881.10.1063/1.457455Search in Google Scholar

Giorgetti, G., Frezzotti, M.L.E., Palmeri, R., and Burke, E.A.J. (1996) Role of fluids in migmatites: CO2-H2O fluid inclusions in leucosomes from the Deep Freeze Range migmatites (Terra Nova Bay, Antarctica). Journal of Metamorphic Geology, 14(3), 307–317.10.1111/j.1525-1314.1996.00307.xSearch in Google Scholar

Gordon, H.R., and McCubbin, T.K. (1966) The 2.8-micron bands of CO2 Journal of Molecular Spectroscopy, 19, 137–154.10.1016/0022-2852(66)90237-2Search in Google Scholar

Guo, H., Chen, Y., Hu, Q., Lu, W., Ou, W., and Geng, L. (2014) Quantitative Raman spectroscopic investigation of geo-fluids high-pressure phase equilibria: Part I. Accurate calibration and determination of CO2 solubility in water from 273.15 to 573.15K and from 10 to 120MPa. Fluid Phase Equilibria, 382, 70–79.10.1016/j.fluid.2014.08.032Search in Google Scholar

Holloway, J.R., Burnham, C.W., and Millhollen, G.L. (1968) Generation of H2O–CO2 mixtures for use in hydrothermal experimentation. Journal of Geophysical Research, 73(20), 6598–6600.10.1029/JB073i020p06598Search in Google Scholar

Hurai, V. (2010) Fluid inclusion geobarometry: Pressure corrections for immiscible H2O–CH4 and H2O–CO2 fluids. Chemical Geology, 278(3–4), 201–211.10.1016/j.chemgeo.2010.09.014Search in Google Scholar

Kawakami, Y., Yamamoto, J., and Kagi, H. (2003) Micro-Raman densimeter for CO2 inclusions in mantle-derived minerals. Applied Spectroscopy, 57(11), 1333–1339.10.1366/000370203322554473Search in Google Scholar

Li, N., Chen, Y-J., Deng, X.-H., and Yao, J.-M. (2014) Fluid inclusion geochemistry and ore genesis of the Longmendian Mo deposit in the East Qinling Orogen: Implication for migmatitic-hydrothermal Momineralization. Ore Geology Reviews, 63, 520–531.10.1016/j.oregeorev.2014.02.005Search in Google Scholar

Lowenstern, J. (2001) Carbon dioxide in magmas and implications for hydrothermal systems. Mineralium Deposita, 36(6), 490–502.10.1007/s001260100185Search in Google Scholar

Mao, S., Duan, Z., and Hu, W. (2009) A vapor–liquid phase equilibrium model for binary CO2–H2O and CH4–H2O systems above 523K for application to fluid inclusions. The Journal of Supercritical Fluids, 50(1), 13–21.10.1016/j.supflu.2009.02.007Search in Google Scholar

Mao, S., Hu, J., Zhang, D., and Li, Y. (2013) Thermodynamic modeling of ternary CH4-H2O-NaCl fluid inclusions. Chemical Geology, 335, 128–135.10.1016/j.chemgeo.2012.11.003Search in Google Scholar

Mumm, A.S., Oberthür, T., Vetter, U., and Blenkinsop, T.G. (1997) High CO2 content of fluid inclusions in gold mineralisations in the Ashanti Belt, Ghana: a new category of ore forming fluids? Mineralium Deposita, 32(2), 107–118.10.1007/s001260050078Search in Google Scholar

Peng, Y., Gu, X., Zhang, Y., Liu, L., Wu, C., and Chen, S. (2014) Ore-forming process of the Huijiabao gold district, southwestern Guizhou Province, China: Evidence from fluid inclusions and stable isotopes. Journal of Asian Earth Sciences, 93, 89–101.10.1016/j.jseaes.2014.06.022Search in Google Scholar

Phillips, G., and Evans, K. (2004) Role of CO2 in the formation of gold deposits. Nature, 429, 860–863.10.1038/nature02644Search in Google Scholar

Rosso, K.M., and Bodnar, R.J. (1995) Microthermometric and Raman spectroscopic detection limits of CO2 in fluid inclusions and the Raman spectroscopic characterization of CO2. Geochimica et Cosmochimica Acta, 59(19), 3961–3975.10.1016/0016-7037(95)94441-HSearch in Google Scholar

Salvioli-Mariani, E., Toscani, L., Boschetti, T., Bersani, D., and Mattioli, M. (2015) Gold mineralisations in the Canan area, Lepaguare District, east-central Honduras: Fluid inclusions and geochemical constraints on gold deposition. Journal of Geochemical Exploration, 158, 243–256.10.1016/j.gexplo.2015.08.003Search in Google Scholar

Schmidt, C., and Ziemann, M.A. (2000) In-situ Raman spectroscopy of quartz: A pressure sensor for hydrothermal diamond-anvil cell experiments at elevated temperatures. American Mineralogist, 85, 1725–1734.10.2138/am-2000-11-1216Search in Google Scholar

Schmidt, C., Rosso, K.M., and Bodnar, R.J. (1995) Synthetic fluid inclusions: XIII. Experimental determination of PVT properties in the system H2O + 40 wt% NaCl + 5 mol% CO2 at elevated temperature and pressure. Geochimica et Cosmochimica Acta, 59(19), 3953–3959.10.1016/0016-7037(95)00258-2Search in Google Scholar

Schmidt, C., Chou, I., Bodnar, R.J., and Bassett, W.A. (1998) Microthermometric analysis of synthetic fluid inclusions in the hydrothermal diamond-anvil cell. American Mineralogist, 83, 995–1007.10.2138/am-1998-9-1007Search in Google Scholar

Seitz, J.C., Pasteris, J.D., and Chou, I.-M. (1996) Raman spectroscopic characterization of gas mixtures. II. Quantitative composition and pressure determination of the CO2-CH4 system. American Journal of Science, 296(6), 577–600.10.2475/ajs.296.6.577Search in Google Scholar

Shmulovich, K.I., and Graham, C.M. (1999) An experimental study of phase equilibria in the system H2O-CO2-NaCl at 800°C and 9 kbar. Contributions to mineralogy and petrology, 136(3), 247–257.10.1007/s004100050536Search in Google Scholar

–––(2004) An experimental study of phase equilibria in the systems H2O–CO2–CaCl2 and H2O–CO2–NaCl at high pressures and temperatures (500–800°C, 0.5–0.9 GPa): Geological and geophysical applications. Contributions to Mineralogy and Petrology, 146(4), 450–462.10.1007/s00410-003-0507-5Search in Google Scholar

Song, Y., Chou, I.M., Hu, W., Robert, B., and Lu, W. (2009) CO2 Density-Raman shift relation derived from synthetic inclusions in fused silica capillaries and its application. Acta Geologica Sinica-English Edition, 83(5), 932–938.10.1111/j.1755-6724.2009.00090.xSearch in Google Scholar

Stoicheff, B.P. (1958) High resolution Raman spectroscopy of gases: XI. Spectra of CS2 and CO2. Canadian Journal of Physics, 36(2), 218–230.10.1139/p58-026Search in Google Scholar

Sun, Q., Zhao, L., Li, N., and Liu, J. (2010) Raman spectroscopic study for the determination of Cl concentration (molarity scale) in aqueous solutions: Application to fluid inclusions. Chemical Geology, 272(1), 55–61.10.1016/j.chemgeo.2010.02.004Search in Google Scholar

Thomas, A.V., and Spooner, E.T.C. (1992) The volatile geochemistry of magmatic H2O-CO2 fluid inclusions from the Tanco zoned granitic pegmatite, southeastern Manitoba, Canada. Geochimica et Cosmochimica Acta, 56(1), 49–65.10.1016/0016-7037(92)90116-ZSearch in Google Scholar

Thomas, A.V., Pasteris, J.D., Bray, C.J., and Spooner, E.T.C. (1990) H2O-CH4-NaCl-CO2 inclusions from the footwall contact of the Tanco granitic pegmatite: Estimates of internal pressure and composition from microthermometry, laser Raman spectroscopy, and gas chromatography. Geochimica et Cosmochimica Acta, 54(3), 559–573.10.1016/0016-7037(90)90353-MSearch in Google Scholar

Tsunogae, T., Santosh, M., Osanai, Y., Owada, M., Toyoshima, T., and Hokada, T. (2002) Very high-density carbonic fluid inclusions in sapphirine-bearing granulites from Tonagh Island in the Archean Napier Complex, East Antarctica: implications for CO2 infiltration during ultrahigh-temperature (T > 1, 100 °C) metamorphism. Contributions to Mineralogy and Petrology, 143(3), 279–299.10.1007/s00410-001-0343-4Search in Google Scholar

Wang, C.H., and Wright, R.B. (1973) Raman studies of the effect of density of the fermi resonance in CO2. Chemical Physics Letters, 23(2), 241–246.10.1016/0009-2614(73)80261-1Search in Google Scholar

Wang, H., and Zheng, H. (2012) Research on Raman spectra of oxalic acid during decarboxylation under high temperature and high pressure. Spectroscopy and Spectral Analysis, 32(3), 669–672.Search in Google Scholar

Wang, G.-G., Ni, P., Wang, R.-C., Zhao, K.-D., Chen, H., Ding, J.-Y., Zhao, C., and Cai, Y.-T. (2013) Geological, fluid inclusion and isotopic studies of the Yinshan Cu–Au–Pb–Zn–Ag deposit, South China: Implications for ore genesis and exploration. Journal of Asian Earth Sciences, 74, 343–360.10.1016/j.jseaes.2012.11.038Search in Google Scholar

Wang, X., Chou, I., Hu, W., Burruss, R.C., Sun, Q., and Song, Y. (2011) Raman spectroscopic measurements of CO2 density: Experimental calibration with high-pressure optical cell (HPOC) and fused silica capillary capsule (FSCC) with application to fluid inclusion observations. Geochimica et Cosmochimica Acta, 75(14), 4080–4093.10.1016/j.gca.2011.04.028Search in Google Scholar

Welsh, H.L., Pashler, P.E., and Stoicheff, B.P. (1952) Density effects in the spectrum of carbon dioxide. Canadian Journal of Physics, 30(2), 99–110.10.1139/p52-009Search in Google Scholar

Williams-Jones, A., and Ferreira, D. (1989) Thermal metamorphism and H2O–CO2–NaCl immiscibility at Patapedia, Quebec: evidence from fluid inclusions. Contributions to Mineralogy and Petrology, 102(2), 247–254.10.1007/BF00375345Search in Google Scholar

Xu, G., and Pollard, P. J. (1999) Origin of CO2-rich fluid inclusions in synorogenic veins from the Eastern Mount Isa Fold Belt, NW Queensland, and their implications for mineralization. Mineralium Deposita, 34(4), 395–404.10.1007/s001260050212Search in Google Scholar

Yamamoto, J., and Kagi, H. (2006) Extended micro-Raman densimeter for CO2 applicable to mantle-originated fluid inclusions. Chemistry Letters, 35(6), 610–611.10.1246/cl.2006.610Search in Google Scholar

Yamamoto, J., Kagi, H., Kawakami, Y., Hirano, N., and Nakamura, M. (2007) Paleo-Moho depth determined from the pressure of CO2 fluid inclusions: Raman spectroscopic barometry of mantle- and crust-derived rocks. Earth and Planetary Science Letters, 253(3-4), 369–377.10.1016/j.epsl.2006.10.038Search in Google Scholar

Zakirov, I., Sretenskaja, N., Aranovich, L., and Volchenkova, V. (2007) Solubility of NaCl in CO2 at high pressure and temperature: First experimental measurements. Geochimica et Cosmochimica Acta, 71(17), 4251–4255.10.1016/j.gca.2007.01.028Search in Google Scholar

Zhu, Y., and Peng, J. (2015) Infrared microthermometric and noble gas isotope study of fluid inclusions in ore minerals at the Woxi orogenic Au–Sb–W deposit, western Hunan, South China. Ore Geology Reviews, 65, 55–69.10.1016/j.oregeorev.2014.08.014Search in Google Scholar

Received: 2015-5-5
Accepted: 2016-10-4
Published Online: 2017-2-9
Published in Print: 2017-2-1

© 2017 by Walter de Gruyter Berlin/Boston

Downloaded on 16.4.2023 from https://www.degruyter.com/document/doi/10.2138/am-2017-5405/html
Scroll to top button