In Situ Quantification of Carbonate Species Concentrations,pH,and pCO 2 in Calcite Fluid Inclusions Using Confocal Raman Spectroscopy

Abstract

Carbonate minerals are globally distributed on the modern and ancient Earth and are abundant in terrestrial and marine depositional environments. Fluid inclusions hosted by calcite retain primary signatures of the source fluid geochemistry at the time of mineral formation (i.e., pCO₂) and can be used to reconstruct paleoenvironments. Confocal laser Raman spectroscopy provides a quick, nondestructive approach to measuring the constituents of fluid inclusions in carbonates and is a reliable method for qualitatively determining composition in both the aqueous and gas phases. Here, we demonstrate a method for accurately quantifying bicarbonate and carbonate ion concentrations (down to 20 mM) and pH (7–11) from calcite fluid inclusions using confocal Raman spectroscopy. Instrument calibrations for carbonate (CO₃^2–) and bicarbonate (HCO₃^–) concentrations and pH were performed using stock solutions. We show that the calcite host mineral does not affect the accurate quantification of carbonate solution concentrations and that these parameters can be used to estimate the pH and pCO₂ of a solution entrapped within a fluid inclusion. We apply the technique to Icelandic spar calcite and find a [CO₃^2–] = 0.11, [HCO₃^–] = 0.17, pH = 10.1, and CO₂ parts per million = 2217. The presence of gaseous Raman bands for CO₂, CH₄, and H₂S suggests that the mineral precipitated in a reducing environment.

Graphical abstract

This is a visual representation of the abstract.

Keywords

Raman spectroscopy fluid inclusions carbonate system pH quantification

Get full access to this article

View all access options for this article.

References

Goldstein

R.H.

. “Clues from Fluid Inclusions”. Science. 2001. 294(5544): 1009–1011. https://doi.org/10.1126/science.1066322

Roedder

. “Introduction to Fluid Inclusions”. Rev. Mineral. 1984. 12: 1–10.

Bodnar

R.J.

. “Introduction to Aqueous-Electrolyte Fluid Inclusions”. In: Samson

Anderson

Marshall

, editors. Fluid Inclusions: Analysis and Interpretation. 32. Ottawa: Mineralogical Association of Canada, 2003. Pp. 81–99.

Diamond

L.W.

. “Systematics of H₂O Inclusions”. In: Samson

Anderson

Marshall

, editors. Fluid Inclusions: Analysis and Interpretation. 32. Ottawa: Mineralogical Association of Canada, 2003. Pp. 5–80.

Frezzotti

M.L.

Tecce

Casagli

. “Raman Spectroscopy for Fluid Inclusion Analysis”. J. Geochem. Explor. 2012. 112: 1–20. https://doi.org/10.1016/j.gexplo.2011.09.009

Mernagh

T.P.

Wilde

A.R.

. “The Use of the Laser Raman Microprobe for the Determination of Salinity in Fluid Inclusions”. Geochim. Cosmochim. Acta. 1989. 53(4): 765–771. https://doi.org/10.1016/0016-7037(89)90022-7

Lowenstein

T.K.

Timofeeff

M.N.

Brennan

S.T.

Hardie

L.A.

Demicco

R.V.

. “Oscillations in Phanerozoic Seawater Chemistry: Evidence from Fluid Inclusions”. Science. 2001. 294(5544): 1086–1088. https://doi.org/10.1126/science.1064280

Sun

Zhao

Liu

. “Raman Spectroscopic Study for the Determination of Cl⁻ Concentration (Molarity Scale) in Aqueous Solutions: Application to Fluid Inclusions”. Chem. Geol. 2010. 272(1–4): 55–61. https://doi.org/10.1016/j.chemgeo.2010.02.004

Azbej

Severs

M.J.

Rusk

B.G.

Bodnar

R.J.

. “In Situ Quantitative Analysis of Individual H₂O–CO₂ Fluid Inclusions by Laser Raman Spectroscopy”. Chem. Geol. 2007. 237(3–4): 255–263. https://doi.org/10.1016/j.chemgeo.2006.06.025

10.

Wopenka

Pasteris

J.D.

. “Raman Intensities and Detection Limits of Geochemically Relevant Gas Mixtures for a Laser Raman Microprobe”. Anal. Chem. 1987. 59(17): 2165–2170. https://doi.org/10.1021/ac00144a034

11.

Dubessy

Poty

Ramboz

. “Advances in C-O-H-N-S Fluid Geochemistry Based on Micro-Raman Spectrometric Analysis of Fluid Inclusions”. Eur. J. Mineral. 1989. 1(4): 517–534.

12.

Dubessy

Boiron

M.-C.

Moissette

Monnin

Sretenskaya

. “Determination of Water, Hydrates, and pH in Fluid Inclusions by Micro-Raman Spectrometry”. Eur. J. Mineral. 1992. 4(5): 885–894.

13.

Burke

E.A.J.

. “Raman Microspectrometry of Fluid Inclusions”. Lithos. 2001. 55(1–4): 139–158. https://doi.org/10.1016/S0024-4937(00)00043-8

14.

Frezzotti

M.L.

Selverstone

Sharp

Z.D.

Compagnoni

. “Carbonate Dissolution During Subduction Revealed by Diamond-Bearing Rocks from the Alps”. Nat. Geosci. 2011. 4(10): 703–706. https://doi.org/10.1038/ngeo1246

15.

Brand

Blamey

Garbelli

Griesshaber

, et al. “Methane Hydrate: Killer Cause of Earth’s Greatest Mass Extinction”. Palaeoworld. 2016. 25(4): 496–507. https://doi.org/10.1016/j.palwor.2016.06.002

16.

Cerling

T.E.

. “Stable Carbon Isotopes in Palaeosol Carbonates”. In: Thiry

Simon-Coinçon

, editors. Palaeoweathering, Palaeosurfaces, and Related Continental Deposits. Oxford, UK: Blackwell Publishing Ltd., 2009. Pp. 43–60. https://doi.org/10.1002/9781444304190.ch2

17.

Griffiths

M.L.

Drysdale

R.N.

Vonhof

H.B.

Gagan

M.K.

, et al. “Younger Dryas–Holocene Temperature and Rainfall History of Southern Indonesia from δ¹⁸O in Speleothem Calcite and Fluid Inclusions”. Earth Planet. Sci. Lett. 2010. 295(1–2): 30–36. https://doi.org/10.1016/j.epsl.2010.03.018

18.

Tabor

Myers

. “Paleosols as Indicators of Paleoenvironment and Paleoclimate”. Annu. Rev. Earth Planet. Sci. 2014. 43(1): 150317182938004. https://doi.org/10.1146/annurev-earth-060614-105355

19.

Schwarcz

H.P.

Harmon

R.S.

Thompson

Ford

D.C.

. “Stable Isotope Studies of Fluid Inclusions in Speleothems and their Paleoclimatic Significance”. Geochim. Cosmochim. Acta. 1976. 40(6): 657–665. https://doi.org/10.1016/0016-7037(76)90111-3

20.

Azmy

Blamey

N.J.F.

. “Source of Diagenetic Fluids from Fluid-Inclusion Gas Ratios”. Chem. Geol. 2013. 347: 246–254. https://doi.org/10.1016/j.chemgeo.2013.04.011

21.

Blamey

Boston

Rosales-Lagarde

. “High-Resolution Signatures of Oxygenation and Microbiological Activity in Speleothem Fluid Inclusions”. Int. J. Speleology. 2016. 45(3): 231–241.

22.

Lüthi

Le Floch

Bereiter

Blunier

, et al. “High-Resolution Carbon Dioxide Concentration Record 650,000–800,000 Years Before Present”. Nature. 2008. 453(7193): 379–382. https://doi.org/10.5038/1827-806X.45.3.1950

23.

Hönisch

Royer

D.L.

Breecker

D.O.

Polissar

P.J.

, et al. “Toward a Cenozoic History of Atmospheric CO₂”. Science. 2023. 382(6675): eadi5177. https://doi.org/10.1126/science.adi5177

24.

Royer

D.L.

Moynihan

K.M.

McKee

M.L.

Londoño

Franks

P.J.

. “Sensitivity of a Leaf Gas-Exchange Model for Estimating Paleoatmospheric CO₂ Concentration”. Clim. Past. 2019. 15(2): 795–809. https://doi.org/10.5194/cp-15-795-2019

25.

Hönisch

Eggins

S.M.

Haynes

L.L.

Allen

K.A.

, et al. Boron Proxies in Paleoceanography and Paleoclimatology. Hoboken, NJ: Wiley-Blackwell, 2019. https://doi.org/10.1002/9781119010678

26.

Breecker

D.O.

. “Quantifying and Understanding the Uncertainty of Atmospheric CO₂ Concentrations Determined from Calcic Paleosols”. Geochem. Geophys. 2013. 14(8): 3210–3220. https://doi.org/10.1002/ggge.20189

27.

Schaller

M.F.

Wright

J.D.

Kent

D.V.

. “Atmospheric pCO₂ Perturbations Associated with the Central Atlantic Magmatic Province”. Science. 2011. 331(6023): 1404–1409. https://doi.org/10.1126/science.1199011

28.

Schaller

M.F.

Wright

J.D.

Kent

D.V.

Olsen

P.E.

. “Rapid Emplacement of the Central Atlantic Magmatic Province as a Net Sink for CO₂”. Earth Planet. Sci. Lett. 2012. 323–324: 27–39. https://doi.org/10.1016/j.epsl.2011.12.028

29.

McElwain

J.C.

Beerling

D.J.

Woodward

F.I.

. “Fossil Plants and Global Warming at the Triassic–Jurassic Boundary”. Science. 1999. 285(5432): 1386–1390. https://doi.org/10.1126/science.285.5432.1386

30.

Schaller

M.F.

Wright

J.D.

Kent

D.V.

. “A 30 Myr Record of Late Triassic Atmospheric pCO₂ Variation Reflects a Fundamental Control of the Carbon Cycle by Changes in Continental Weathering”. Geol. Soc. Am. Bull. 2015. 127(5–6): 661–671. https://doi.org/10.1130/B31107.1

31.

Diamond

L.W.

. “Review of the Systematics of CO₂–H₂O Fluid Inclusions”. Lithos. 2001. 55(1–4): 69–99. https://doi.org/10.1016/S0024-4937(00)00039-6

32.

Zimmermann

J.L.

Moretto

. “Release of Water and Gases from Halite Crystals”. Eur. J. Mineral. 1996. 8(2): 413–422.

33.

Norman

D.I.

Blamey

Moore

J.N.

. “Interpreting Geothermal Process and Fluid Sources from Fluid Inclusion Organic Compounds and CO₂/N₂ Ratios”. Paper presented at: Twenty-Seventh Workshop on Geothermal Reservoir Engineering. Stanford University, Stanford, California; 28–30 January 2002.

34.

Williams

A.E.

. “Mass Spectrometric Analysis of Volatiles in Fluid Inclusions: Aliquot Calibration Valve to Simulate Inclusion Rupture”. Chem. Geol. 1996. 131(1): 155–165. https://doi.org/10.1016/0009-2541(96)00064-2

35.

Fries

Steele

. “Raman Spectroscopy and Confocal Raman Imaging in Mineralogy and Petrography”. In: Toporski

Dieing

Hollricher

, editors. Confocal Raman Microscopy. New York: Springer Link, 2011. Pp. 209–236. https://doi.org/10.1007/978-3-319-75380-5_10

36.

Butler

J.N.

. Carbon Dioxide Equilibria and their Applications. Reading, MA: Addison-Wesley, 1982.

37.

Hrstka

Dubessy

Zachariáš

. “Bicarbonate-Rich Fluid Inclusions and Hydrogen Diffusion in Quartz from the Libčice Orogenic Gold Deposit, Bohemian Massif”. Chem. Geol. 2011. 281(3–4): 317–332. https://doi.org/10.1016/j.chemgeo.2010.12.018

38.

Facq

Daniel

Montagnac

Cardon

Sverjensky

D.A.

. “In Situ Raman Study and Thermodynamic Model of Aqueous Carbonate Speciation in Equilibrium with Aragonite under Subduction Zone Conditions”. Geochim. Cosmochim. Acta. 2014. 132: 375–390. https://doi.org/10.1016/j.gca.2014.01.030

39.

Oliver

B.G.

Davis

A.R.

. “Vibrational Spectroscopic Studies of Aqueous Alkali Metal Bicarbonate and Carbonate Solutions”. Can. J. Chem. 1973. 51(5): 698–702. https://doi.org/10.1139/v73-106

40.

Rudolph

W.W.

Fischer

Irmer

. “Vibrational Spectroscopic Studies and Density Functional Theory Calculations of Speciation in the CO₂–Water System”. Appl. Spectrosc. 2006. 60(2): 130–144. https://doi.org/10.1366/000370206776023421

41.

Rudolph

W.W.

Irmer

Königsberger

. “Speciation Studies in Aqueous HCO₃⁻– CO₃²⁻ Solutions. A Combined Raman Spectroscopic and Thermodynamic Study”. Dalton Trans. RSC. 2008. 7: 900–908. https://doi.org/10.1039/B713254A

42.

Caumon

M.-C.

Tarantola

Mosser-Ruck

. “Raman Spectra of Water in Fluid Inclusions: I. Effect of Host Mineral Birefringence on Salinity Measurement”. J. Raman Spectrosc. 2015. 46(10): 969–976. https://doi.org/10.1002/jrs.4708

43.

Frantz

J.D.

. “Raman Spectra of Potassium Carbonate and Bicarbonate Aqueous Fluids at Elevated Temperatures and Pressures: Comparison with Theoretical Simulations”. Chem. Geol. 1998. 152(3–4): 211–225. https://doi.org/10.1016/S0009-2541(98)00058-8

44.

Zheng

. “Quantitative Measurement of the Concentration of Sodium Carbonate in the System of Na₂CO₃–H₂O by Raman Spectroscopy”. Chem. Geol. 2010. 273(3): 267–271. https://doi.org/10.1016/j.chemgeo.2010.03.001

45.

Sun

Qin

. “Raman OH Stretching Band of Water as an Internal Standard to Determine Carbonate Concentrations”. Chem. Geol. 2011. 283(3–4): 274–278. https://doi.org/10.1016/j.chemgeo.2011.01.025

46.

Chave

K.E.

. “Evidence on History of Sea Water from Chemistry of Deeper Subsurface Waters of Ancient Basins”. Am. Assoc. Pet. Geol. Bull. 1960. 44(3): 357–370. https://doi.org/10.1306/0BDA5FF3-16BD-11D7-8645000102C1865D

47.

Mackenzie

F.T.

Garrels

R.M.

. “Chemical Mass Balance Between Rivers and Oceans”. Am. J. Sci. 1966. 264(7): 507–525. https://doi.org/10.2475/ajs.264.7.507

48.

Garrels

R.M.

Mackenzie

. “Origin of the Chemical Compositions of Some Springs and Lakes”. Adv. Chem. 1967. 67: 222–242. https://doi.org/10.1021/ba-1967-0067.ch010

49.

Burley

S.D.

Mullis

Matter

. “Timing Diagenesis in the Tartan Reservoir (UK North Sea): Constraints from Combined Cathodoluminescence Microscopy and Fluid Inclusion Studies”. Mar. and Petrol. Geol. 1989. 6(2): 98–120. https://doi.org/10.1016/0264-8172(89)90014-7

50.

Stumm

Morgan

J.J.

. Aquatic Chemistry: Chemical Equilibria and Rates in Natural Waters. Hoboken, NJ: Wiley, 1996.

51.

Langmuir

. Aqueous Environmental Geochemistry. Upper Saddle River, NJ: Prentice Hall, 1997.

52.

Sumner

M.E.

. Handbook of Soil Science. Boca Raton, Florida: CRC Press, 1999.

53.

Millero

F.J.

Graham

T.B.

Huang

Bustos-Serrano

Pierrot

. “Dissociation Constants of Carbonic Acid in Seawater as a Function of Salinity and Temperature”. Mar. Chem. 2006. 100(1–2): 80–94. https://doi.org/10.1016/j.marchem.2005.12.001

54.

Onda

Sada

Kobayashi

Kito

Ito

. “Salting-Out Parameters of Gas Solubility in Aqueous Salt Solutions”. J. Chem. Eng. Jpn. 1970. 3(1): 18–24. https://doi.org/10.1252/jcej.3.18

55.

Hurowitz

Catling

D.C.

Woodward

W.W.

, High Carbonate Alkalinity Lakes on Mars and their Potential Role in an Origin of Life Beyond Earth“. Elements. 2023. 19: 37-44. https://doi.org/10.2138/gselements.19.1.37

56.

Butler

J.N.

. Ionic Equilibrium: Solubility and pH Calculations. New York: Wiley, 1998.

57.

Drever

J.I.

. The Geochemistry of Natural Waters: Surface and Groundwater Environments. Upper Saddle River, NJ: Prentice Hall, 1997.

58.

Dieing

Hollricher

. “High-Resolution, High-Speed Confocal Raman Imaging”. Vib. Spectrosc. 2008. 48(1): 22–27. https://doi.org/10.1016/j.vibspec.2008.03.004

59.

Davis

A.R.

Oliver

B.G.

. “A Vibrational-Spectroscopic Study of the Species Present in the CO₂–H₂O System”. J. Solution Chem. 1972. 1(4): 329–339. https://doi.org/10.1007/BF00715991

60.

Pasteris

J.D.

Beyssac

. “Welcome to Raman Spectroscopy: Successes, Challenges, and Pitfalls”. Elements. 2020. 16(2): 87–92. https://doi.org/10.2138/gselements.16.2.87

61.

Giridhar

Manepalli

R.R.K.N.

Apparao

. “Confocal Raman Spectroscopy”. In: Thomas

Thomas

Zachariah

A.K.

, editors. Spectroscopic Methods for Nanomaterials Characterization. Amsterdam: Elsevier, 2017. Pp. 141–161. https://doi.org/10.1016/B978-0-323-46140-5.00007-8

62.

Goldstein

R.H.

. “Petrographic Analysis of Fluid Inclusions”. In: Samson

Anderson

Marshall

, editors. Fluid Inclusions: Analysis and Interpretation. 32. Ottawa, Canada: Mineralogy Association of Canada, 2003. Pp. 1–43. https://doi.org/10.3749/9780921294672.ch02

63.

Rosso

K.M.

Bodnar

R.J.

. “Microthermometric and Raman Spectroscopic Detection Limits of CO₂ in Fluid Inclusions and the Raman Spectroscopic Characterization of CO₂”. Geochim. Cosmochim. Acta. 1995. 59(19): 3961–3975. https://doi.org/10.1016/0016-7037(95)94441-H

64.

Kawakami

Yamamoto

Kagi

. “Micro-Raman Densimeter for CO₂ Inclusions in Mantle-Derived Minerals”. Appl. Spectrosc. 2003. 57(11): 1333–1339. https://doi.org/10.1366/000370203322554473

65.

Wang

Chou

I.-M.

. “Raman Spectroscopic Characterization on the OH Stretching Bands in NaCl–Na₂CO₃–Na₂SO₄–CO₂–H₂O Systems: Implications for the Measurement of Chloride Concentrations in Fluid Inclusions”. J. Geochem. Explor. 2013. 132: 111–119. https://doi.org/10.1016/j.gexplo.2013.06.006

66.

Carroll

J.J.

Slupsky

J.D.

Mather

A.E.

. “The Solubility of Carbon Dioxide in Water at Low Pressure”. J. Phys. Chem. Ref. Data. 1991. 20(6): 1201–1209. https://doi.org/10.1063/1.555900

67.

Wiebe

Gaddy

V.L.

. “The Solubility of Carbon Dioxide in Water at Various Temperatures from 12 to 40° and at Pressures to 500 Atmospheres. Critical Phenomena”. J. Am. Chem. Soc. 1940. 62(4): 815–817. https://doi.org/10.1021/ja01861a033

68.

Zeebe

R.E.

Wolf-Gladrow

. CO₂ in Seawater: Equilibrium, Kinetics, Isotopes. Amsterdam: Elsevier, 2001.

69.

Pelletier

M.J.

. Analytical Applications of Raman Spectroscopy. Oxford: Blackwell Publishing, 1999.