Chemistry:Melt inclusion

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Multiple melt inclusions in an olivine crystal. Individual inclusions are oval or round in shape and consist of clear glass, together with a small round vapor bubble and in some cases a small square spinel crystal. The black arrow points to one good example, but there are several others. The occurrence of multiple inclusions within a single crystal is relatively common

A melt inclusion is a small parcel or "blobs" of melt(s) that is entrapped by crystals growing[1] in magma and eventually forming igneous rocks. In many respects it is analogous to a fluid inclusion within magmatic hydrothermal systems.[2][3] Melt inclusions tend to be microscopic in size and can be analyzed for volatile contents that are used to interpret trapping pressures of the melt at depth.

Characteristics

Melt inclusions are generally small - most are less than 80 micrometres across (a micrometre is one thousandth of a millimeter, or about 0.00004 inches).[4] They may contain a number of different constituents, including glass (which represents melt that has been quenched by rapid cooling), small crystals and a separate vapour-rich bubble.[5] They occur in the crystals that can be found in igneous rocks, such as for example quartz, feldspar, olivine, pyroxene, nepheline, magnetite, perovskite and apatite.[6][7][8] Melt inclusions can be found in both volcanic and plutonic rocks. In addition, melt inclusions can contain immiscible (non-miscible) melt phases and their study is an exceptional way to find direct evidence for presence of two or more melts at entrapment.[5]

Analysis

Although they are small, melt inclusions can provide an abundance of useful information. Using microscopic observations and a range of chemical microanalysis techniques geochemists and igneous petrologists can obtain a range of unique information from melt inclusions. There are various techniques used in analyzing melt inclusion H2O and CO2 contents, major, minor and trace elements including double-sided FTIR micro transmittance,[9] single-sided FTIR micro reflectance,[10] Raman spectroscopy,[11] microthermometry,[12] Secondary Ion Mass Spectroscopy (SIMS), Laser Ablation-Inductively Coupled Plasma Mass Spectrometry (LA-ICPMS), Scanning Electron Microscopy (SEM) and electron microprobe analysis (EMPA).[13] If there is a vapor bubble present within the melt inclusion, analysis of the vapor bubble must be taken into consideration when reconstructing the total volatile budget of the melt inclusion.[14]

Microthermometry

Microthermometry is the process of reheating a melt inclusion to its original melt temperature and then rapidly quenching to form a homogenous glass phase free of daughter minerals or vapor bubbles that may have been originally contained within the melt inclusion.[15]

Microscope-mounted high temperature stage heating

Stage heating is the process of heating a melt inclusion on a microscope-mounted stage and flowing either helium gas (Vernadsky stage)[16][17] or argon gas (Linkam TS1400XY)[18] over the stage and then rapidly quenching the melt inclusion after it has reached its original melt temperature to form a homogenous glass phase. Use of a heating stage allows for observation of changing phases of the melt inclusion as it is reheated to its original melt temperature.[19]

One atmosphere vertical furnaces

This process allows for reheating of one or more melt inclusions in a furnace held at a constant pressure of one atmosphere to their original melt temperatures and then rapidly quenching in water to produce a homogenous glass phase.[20]

Fourier transform infrared spectroscopy (FTIR)

FTIR is an analytical method which uses an infrared laser focused on a spot on the glass phase of the melt inclusion to determine an absorption (or extinction) coefficient for either H2O and CO2 associated with wavelengths for each species depending on the parent lithology that contained the melt inclusion.[10][21]

Raman spectroscopy

Raman spectroscopy is similar to FTIR in using a focused laser on the glass phase of the melt inclusion[22][23] or a vapor bubble[24] that may be contained in the melt inclusion to identify wavelengths associated with the Raman vibrating bands of volatiles, such as H2O and CO2. Raman spectroscopy can also be used to determine the density of CO2 contained in a vapor bubble if present at a high enough concentration within a melt inclusion.[11]

Secondary Ion Mass Spectrometry (SIMS)

SIMS is used to determine volatile and trace element concentrations by aiming an ion beam (16O or 133Cs+) at the melt inclusion to produce secondary ions that can be measured by a mass spectrometer.[25]

Laser Ablation-Inductively Coupled Plasma Mass Spectrometry (LA-ICPMS)

LA-ICP-MS can determine major and trace elements, however, with LA-ICPMS, the melt inclusion and any accompanying materials within the melt inclusion are ionized, thus destroying the melt inclusion, and then analyzed with a mass spectrometer.[26][27]

Scanning Electron Microscopy (SEM)

Scanning electron microscopy is a useful tool to employ before any of the above analyses that may result in loss of the original material since it can be used to check for daughter minerals or vapor bubbles and help determine the best technique that should be chosen for melt inclusion analysis.[4]

Electron Microprobe Analysis (EPMA)

Electron microprobe analysis is ubiquitous in the analysis of major and minor elements in melt inclusions and provide oxide concentrations used in determining parental magma types of the melt inclusions and phenocryst hosts.[28]

X-ray microtomography

Melt inclusions have been imaged in three dimensions using X-ray microtomography.[29] This method can be used to determine the dimensions of different phases present in melt inclusions more precisely than by using visible light microscopy.

Interpretation

Volatile Concentrations

Melt inclusions can be used to determine the composition, compositional evolution and volatile components[14] of magmas that existed in the history of magma systems. This is because melt inclusions act as a tiny pressure vessel that isolates and preserves the ambient melt surrounding the crystal before they are modified by later processes, such as post-entrapment crystallization.[4] Given that melt inclusions form at varying pressures (P) and temperatures (T), they can also provide important information about the entrapping conditions (P-T) at depth and their volatile contents (H2O, CO2, S, Cl and F) that drive volcanic eruptions.[21]

Vapor Bubbles

Melt inclusion with accompanying vapor bubble from an olivine crystal. Collected from ash related to the 1992 eruption of Cerro Negro Volcano, Nicaragua
Animation of a melt inclusion viewed in transmitted light.

The presence of a vapor bubble adds an additional component for analysis given that the vapor bubble could contain a significant proportion of the H2O and CO2 originally in the melt sampled by the melt inclusion.[16][30] If the vapor bubble is composed primarily of CO2, Raman spectroscopy can be used to determine the density of CO2 present.[31][11]

Major, minor and trace element concentrations

Major and minor element concentrations are generally determined using EPMA and common element compositions include Si, Ti, Al, Cr, Fe, Mn, Mg, Ca, Ni, Na, K, P, Cl, F and S.[32] Knowledge of the oxide concentrations related to these major and minor elements can help to determine the composition of the parental magma, the melt inclusion and the phenocryst hosts.[28]

Trace element concentrations can be measured by SIMS analysis with resolution in some cases as low as 1 ppm.[33] LA-ICPMS analyses can also be used to determine trace element concentrations, however lower resolution compared to SIMS does not provide determination of concentrations as low as 1 ppm.[5]

History

Henry Clifton Sorby, in 1858, was the first to document microscopic melt inclusions in crystals.[34] The study of melt inclusions has been driven more recently by the development of sophisticated chemical analysis techniques. Scientists from the former Soviet Union lead the study of melt inclusions in the decades after World War II,[35] and developed methods for heating melt inclusions under a microscope, so changes could be directly observed. A.T. Anderson explored analysis of melt inclusions from basaltic magmas from Kilauea Volcano in Hawaii to determine initial volatile concentrations of magma at depth.[36]

See also

References

  1. Roedder, Edwin (1979). "Origin and significance of magmatic inclusions". Bulletin de Mineralogie 102 (5): 487–510. 
  2. Roedder, Edwin (1984). "Fluid Inclusions". Reviews in Mineralogy 12: 644. 
  3. Becker, S.P.; Bodnar, R.J.; Reynolds, T.J. (2019). "Temporal and spatial variations in characteristics of fluid inclusions in epizonal magmatic-hydrothermal systems: Applications in exploration for porphyry copper deposits" (in en). Journal of Geochemical Exploration 204: 240–255. doi:10.1016/j.gexplo.2019.06.002. 
  4. 4.0 4.1 4.2 Cannatelli, C.; Doherty, A.L.; Esposito, R.; Lima, A.; De Vivo, B. (2016). "Understanding a volcano through a droplet: A melt inclusion approach" (in en). Journal of Geochemical Exploration 171: 4–19. doi:10.1016/j.gexplo.2015.10.003. 
  5. 5.0 5.1 5.2 Kent, A. J.R. (2008). "Melt Inclusions in Basaltic and Related Volcanic Rocks" (in en). Reviews in Mineralogy and Geochemistry 69 (1): 273–331. doi:10.2138/rmg.2008.69.8. ISSN 1529-6466. Bibcode2008RvMG...69..273K. https://pubs.geoscienceworld.org/rimg/article/69/1/273-331/289110. 
  6. Abersteiner, Adam; Giuliani, Andrea; Kamenetsky, Vadim S.; Phillips, David (2017). "Petrographic and melt-inclusion constraints on the petrogenesis of a magmaclast from the Venetia kimberlite cluster, South Africa" (in en). Chemical Geology 455: 331–341. doi:10.1016/j.chemgeo.2016.08.029. Bibcode2017ChGeo.455..331A. 
  7. Tollan, Peter; Ellis, Ben; Troch, Juliana; Neukampf, Julia (2019). "Assessing magmatic volatile equilibria through FTIR spectroscopy of unexposed melt inclusions and their host quartz: a new technique and application to the Mesa Falls Tuff, Yellowstone" (in en). Contributions to Mineralogy and Petrology 174 (3): 24. doi:10.1007/s00410-019-1561-y. ISSN 0010-7999. Bibcode2019CoMP..174...24T. http://link.springer.com/10.1007/s00410-019-1561-y. 
  8. Chang, Jia; Audétat, Andreas (2020). "LA-ICP-MS analysis of crystallized melt inclusions in olivine, plagioclase, apatite and pyroxene: quantification strategies and effects of post-entrapment modifications" (in en). Journal of Petrology 62 (4): egaa085. doi:10.1093/petrology/egaa085. ISSN 0022-3530. https://academic.oup.com/petrology/advance-article/doi/10.1093/petrology/egaa085/5897417. 
  9. Mironov, N. L.; Portnyagin, M. V. (2011). "H2O and CO2 in parental magmas of Kliuchevskoi volcano inferred from study of melt and fluid inclusions in olivine" (in en). Russian Geology and Geophysics. Melts and Fluids in Natural Mineral and Ore Formation Processes: Modern Studies of Fluid and Melt Inclusions in Minerals 52 (11): 1353–1367. doi:10.1016/j.rgg.2011.10.007. ISSN 1068-7971. Bibcode2011RuGG...52.1353M. http://www.sciencedirect.com/science/article/pii/S1068797111002161. 
  10. 10.0 10.1 King, P. L.; Larsen, J. F. (2013). "A micro-reflectance IR spectroscopy method for analyzing volatile species in basaltic, andesitic, phonolitic, and rhyolitic glasses" (in en). American Mineralogist 98 (7): 1162–1171. doi:10.2138/am.2013.4277. ISSN 0003-004X. Bibcode2013AmMin..98.1162K. https://pubs.geoscienceworld.org/ammin/article/98/7/1162-1171/45886. 
  11. 11.0 11.1 11.2 Moore, L. R.; Gazel, E.; Tuohy, R.; Lloyd, A. S.; Esposito, R.; Steele-MacInnis, M.; Hauri, E. H.; Wallace, P. J. et al. (2015). "Bubbles matter: An assessment of the contribution of vapor bubbles to melt inclusion volatile budgets" (in en). American Mineralogist 100 (4): 806–823. doi:10.2138/am-2015-5036. ISSN 0003-004X. Bibcode2015AmMin.100..806M. https://pubs.geoscienceworld.org/ammin/article/100/4/806-823/40390. 
  12. Mironov, N.L.; Tobelko, D.P.; Smirnov, S.Z.; Portnyagin, M.V.; Krasheninnikov, S.P. (2020). "ESTIMATION OF CO2 CONTENT IN THE GAS PHASE OF MELT INCLUSIONS USING RAMAN SPECTROSCOPY: CASE STUDY OF INCLUSIONS IN OLIVINE FROM THE KARYMSKY VOLCANO (Kamchatka)". Russian Geology and Geophysics 61 (5): 600–610. doi:10.15372/RGG2019169. Bibcode2020RuGG...61..600M. http://sibran.ru/en/journals/issue.php?ID=179087&ARTICLE_ID=179095. 
  13. Hartley, Margaret E.; Bali, Enikö; Maclennan, John; Neave, David A.; Halldórsson, Sæmundur A. (2018). "Melt inclusion constraints on petrogenesis of the 2014–2015 Holuhraun eruption, Iceland" (in en). Contributions to Mineralogy and Petrology 173 (2): 10. doi:10.1007/s00410-017-1435-0. ISSN 0010-7999. PMID 31983759. Bibcode2018CoMP..173...10H. 
  14. 14.0 14.1 Wallace, P. J.; Kamenetsky, V. S.; Cervantes, P. (2015). "Melt inclusion CO2 contents, pressures of olivine crystallization, and the problem of shrinkage bubbles" (in en). American Mineralogist 100 (4): 787–794. doi:10.2138/am-2015-5029. ISSN 0003-004X. Bibcode2015AmMin.100..787W. https://pubs.geoscienceworld.org/ammin/article/100/4/787-794/40385. 
  15. Danyushevsky, Leonid V; McNeill, Andrew W; Sobolev, Alexander V (2002). "Experimental and petrological studies of melt inclusions in phenocrysts from mantle-derived magmas: an overview of techniques, advantages and complications" (in en). Chemical Geology 183 (1–4): 5–24. doi:10.1016/S0009-2541(01)00369-2. Bibcode2002ChGeo.183....5D. https://eprints.utas.edu.au/681/1/CG2002.pdf. 
  16. 16.0 16.1 Esposito, Rosario; Lamadrid, Hector M.; Redi, Daniele; Steele-MacInnis, Matthew; Bodnar, Robert J.; Manning, Craig E.; De Vivo, Benedetto; Cannatelli, Claudia et al. (2016). "Detection of liquid H 2 O in vapor bubbles in reheated melt inclusions: Implications for magmatic fluid composition and volatile budgets of magmas?" (in en). American Mineralogist 101 (7): 1691–1695. doi:10.2138/am-2016-5689. ISSN 0003-004X. Bibcode2016AmMin.101.1691E. https://pubs.geoscienceworld.org/ammin/article/101/7/1691-1695/284058. 
  17. Sobolev, A.V.; Dmitriev, L.V.; Baruskov, V.L.; Nevsorov, V.N.; Slutsky, A.B. (1980). "The formation conditions of high-magnesian olivine from the monomineralic fraction of Luna 24 regolith. Proceedings of the Apollo 11 Lunar Science Conference". Geochimica et Cosmochimica Acta Supplement I: 105–116. 
  18. MacDonald, A.J.; Spooner, E.T.C. (1981). "Calibration of a Linkam TH 600 programmable heating-cooling stage for microthermometric examination of fluid inclusions". Economic Geology 76 (5): 1248–1258. doi:10.2113/gsecongeo.76.5.1248. 
  19. Esposito, R.; Klebesz, R.; Bartoli, O.; Klyukin, Y.; Moncada, D.; Doherty, A.; Bodnar, R. (2012). "Application of the Linkam TS1400XY heating stage to melt inclusion studies". Open Geosciences 4 (2): 208–218. doi:10.2478/s13533-011-0054-y. Bibcode2012CEJG....4..208E. 
  20. Schiano, Pierre (2003). "Primitive mantle magmas recorded as silicate melt inclusions in igneous minerals" (in en). Earth-Science Reviews 63 (1–2): 121–144. doi:10.1016/S0012-8252(03)00034-5. Bibcode2003ESRv...63..121S. 
  21. 21.0 21.1 Metrich, N.; Wallace, P. J. (2008). "Volatile Abundances in Basaltic Magmas and Their Degassing Paths Tracked by Melt Inclusions" (in en). Reviews in Mineralogy and Geochemistry 69 (1): 363–402. doi:10.2138/rmg.2008.69.10. ISSN 1529-6466. Bibcode2008RvMG...69..363M. https://pubs.geoscienceworld.org/rimg/article/69/1/363-402/289118. 
  22. Thomas, Rainer; Davidson, Paul (2012). "The application of Raman spectroscopy in the study of fluid and melt inclusions" (in en). Zeitschrift der Deutschen Gesellschaft für Geowissenschaften 163 (2): 113–126. doi:10.1127/1860-1804/2012/0163-0113. ISSN 1860-1804. http://www.schweizerbart.de/papers/zdgg/detail/163/78219/The_application_of_Raman_spectroscopy_in_the_study?af=crossref. 
  23. Severs, M.J.; Azbej, T.; Thomas, J.B.; Mandeville, C.W.; Bodnar, R.J. (2007). "Experimental determination of H2O loss from melt inclusions during laboratory heating: Evidence from Raman spectroscopy" (in en). Chemical Geology 237 (3–4): 358–371. doi:10.1016/j.chemgeo.2006.07.008. Bibcode2007ChGeo.237..358S. 
  24. Behrens, Harald; Roux, Jacques; Neuville, Daniel R.; Siemann, Michael (2006). "Quantification of dissolved H2O in silicate glasses using confocal microRaman spectroscopy" (in en). Chemical Geology 229 (1–3): 96–112. doi:10.1016/j.chemgeo.2006.01.014. Bibcode2006ChGeo.229...96B. 
  25. Hauri, Erik (2002). "SIMS analysis of volatiles in silicate glasses, 2: isotopes and abundances in Hawaiian melt inclusions" (in en). Chemical Geology 183 (1–4): 115–141. doi:10.1016/S0009-2541(01)00374-6. Bibcode2002ChGeo.183..115H. 
  26. Pettke, Thomas; Halter, Werner E.; Webster, James D.; Aigner-Torres, Mario; Heinrich, Christoph A. (2004). "Accurate quantification of melt inclusion chemistry by LA-ICPMS: a comparison with EMP and SIMS and advantages and possible limitations of these methods" (in en). Lithos 78 (4): 333–361. doi:10.1016/j.lithos.2004.06.011. Bibcode2004Litho..78..333P. 
  27. Tucker, Jonathan M.; Hauri, Erik H.; Pietruszka, Aaron J.; Garcia, Michael O.; Marske, Jared P.; Trusdell, Frank A. (2019). "A high carbon content of the Hawaiian mantle from olivine-hosted melt inclusions" (in en). Geochimica et Cosmochimica Acta 254: 156–172. doi:10.1016/j.gca.2019.04.001. Bibcode2019GeCoA.254..156T. 
  28. 28.0 28.1 Venugopal, Swetha; Moune, Séverine; Williams-Jones, Glyn (2016). "Investigating the subsurface connection beneath Cerro Negro volcano and the El Hoyo Complex, Nicaragua" (in en). Journal of Volcanology and Geothermal Research 325: 211–224. doi:10.1016/j.jvolgeores.2016.06.001. Bibcode2016JVGR..325..211V. 
  29. Richard, Antonin; Morlot, Christophe; Créon, Laura; Beaudoin, Nicolas; Balistky, Vladimir; Pentelei, Svetlana; Dyja-Person, Vanessa; Giuliani, Gaston et al. (2019). "Advances in 3D imaging and volumetric reconstruction of fluid and melt inclusions by high resolution X-ray computed tomography". Chemical Geology 508: 3–14. doi:10.1016/j.chemgeo.2018.06.012. 
  30. Aster, Ellen M.; Wallace, Paul J.; Moore, Lowell R.; Watkins, James; Gazel, Esteban; Bodnar, Robert J. (2016). "Reconstructing CO2 concentrations in basaltic melt inclusions using Raman analysis of vapor bubbles" (in en). Journal of Volcanology and Geothermal Research 323: 148–162. doi:10.1016/j.jvolgeores.2016.04.028. Bibcode2016JVGR..323..148A. 
  31. Steele-Macinnis, M.; Esposito, R.; Bodnar, R. J. (2011). "Thermodynamic Model for the Effect of Post-entrapment Crystallization on the H2O-CO2 Systematics of Vapor-saturated, Silicate Melt Inclusions" (in en). Journal of Petrology 52 (12): 2461–2482. doi:10.1093/petrology/egr052. ISSN 0022-3530. 
  32. Straub, Susanne M.; Layne, Graham D. (2003). "The systematics of chlorine, fluorine, and water in Izu arc front volcanic rocks: Implications for volatile recycling in subduction zones" (in en). Geochimica et Cosmochimica Acta 67 (21): 4179–4203. doi:10.1016/S0016-7037(03)00307-7. Bibcode2003GeCoA..67.4179S. 
  33. Audetat, A.; Lowenstern, J.B.; Turekian, H.D.; Holland, K.K. (2014). Treatise on Geochemistry (Second ed.). Oxford: Elsevier. pp. 143–173. ISBN 978-0-08-098300-4. 
  34. Sorby, H. C. (1858). "On the microscopic structures of crystals, indicating the origin of minerals and rocks". Geological Society of London Quarterly Journal 14 (1–2): 453–500. doi:10.1144/GSL.JGS.1858.014.01-02.44. 
  35. V. S., Sobolev; Kostyuk, V. P. (1975). "Magmatic crystallization based on a study of melt inclusions". Fluid Inclusion Research 9: 182–235. 
  36. Anderson, A.T.; Wright, T.L. (1972). "Phenocrysts and glass inclusions and their bearing on oxidation and mixing of basaltic magmas, Kilauea Volcano, Hawaii". American Mineralogist 57: 188–216. 

Further reading

  • Roedder, Edwin (1979). "Origin and significance of magmatic inclusions". Bulletin de Mineralogie 102 (5): 487–510. 
  • Roedder, Edwin (1984). "Fluid Inclusions". Reviews in Mineralogy 12: 644. 
  • Frezzotti, Maria-Luce (January 2001). "Silicate-melt inclusions in magmatic rocks: applications to petrology". Lithos 55 (1–4): 273–299. doi:10.1016/S0024-4937(00)00048-7. Bibcode2001Litho..55..273F. 
  • Lowenstern, J. B. (1995). "Applications of silicate melt inclusions to the study of magmatic volatiles". Magmas, Fluid and Ore Deposits. Mineralogical Association of Canada Short Course. 23. pp. 71–99. 
  • Melt Inclusions in Volcanic Systems: Methods, Applications and Problems. Elsevier. 2003. ISBN 9780080536101. 

External links