A NMR and molecular dynamics study of CO2-bearing basaltic melts and glasses

• Published in: Chemical geology Vol. 418; pp. 89 - 103
• Main Authors: Morizet, Y., Vuilleumier, R., Paris, M.
• Format: Journal Article
• Language: English
• Published: Elsevier B.V 15-12-2015; Elsevier
• Subjects: Aluminosilicate network speciation; Aluminum; Carbon dioxide; CO2 speciation; Coordination numbers; First-principles molecular dynamics simulations; Glass; High temperature melt versus glass; MAS NMR; Melts; Molecular dynamics; Sciences of the Universe; Silicon; Simulation; High temperature melt versus glass; CO2 speciation; Aluminosilicate network speciation; First-principles molecular dynamics simulations; MAS NMR
• ISSN: 0009-2541; 1872-6836
• DOI: 10.1016/j.chemgeo.2015.03.021

The presence of volatile, especially carbon dioxide (CO2), in silicate liquids is considered as a key parameter to magmatic degassing and eruptive processes. Unfortunately, due to experimental difficulties, our current knowledge on the CO2 effect on silicate melt structure is weak and relies on the observation of ex-situ recovered CO2-bearing glasses.
In the present work, we confront the results obtained from NMR spectroscopic observations of glass synthesised at pressure between 0.5 and 3.0GPa and theoretical investigations from first-principles molecular dynamics (FPMD) simulations conducted at 5.0 and 8.0GPa on high temperature melt for a simplified basaltic composition.
The results obtained on the aluminosilicate framework (molar fraction of silicon species and Al average coordination number) suggest that both ex-situ and in-situ results compare adequately. The results are in agreement with our current knowledge on the change in aluminosilicate melt/glass structure with changing intensive conditions. Increasing pressure from 0.5 to 8.0GPa induces 1) an increase in the average Al coordination number from 4.1 to almost 5.0 and 2) an increase in the degree of polymerisation with NBO/Si changing from 1.30 to 0.80.
The presence of CO2 does not seem to induce a dramatic change on both the average Al coordination number and the NBO/Si. FPMD simulations performed with 0 and 20wt.% CO2 at 8.0GPa result in a change from 4.84 to 4.96 for the average Al coordination number and in a change from 0.87 to 0.80 for the NBO/Si value, respectively.
On the contrary, there is a lack of consistency in between the CO2 speciation obtained from NMR spectroscopy and from FPMD simulations. Whereas the analysis of glasses does not reveal the presence of CO2mol species, the FPMD simulation results suggests the existence of a small proportion of CO2mol. Further work with in-situ experimental approach is therefore required to explain the observed lack of consistency between the CO2 speciation in glass and in high temperature melt with basaltic composition.
•CO2-bearing haplo-basaltic glass and high temperature melt have comparable aluminosilicate molecular structure.•For haplo-basaltic composition, CO2mol species is present in the high temperature melt but absent in the equivalent glass.•CO2 has a limited effect on aluminosilicate network molecular structure.