Solubility and solution mechanisms of NOH volatiles in silicate melts at high pressure and temperature - Amine groups and hydrogen fugacity

Bjorn O. Mysen, Shigeru Yamashita, Nadezda Chertkova

Research output: Contribution to journalArticle

40 Citations (Scopus)

Abstract

The solubility and solution mechanisms of nitrogen in silicate melts have been examined via nitrogen analyses and vibrational spectroscopy (Raman and FTIR). Pressure (P), temperature (T), hydrogen fugacity (fH2), and silicate melt composition (degree of melt polymerization) were independent variables in experiments in the 1-2.5 GPa pressure and 1300-4500 °C temperature ranges. The fH2 was controlled at values defined by the magnetite-hematite (MH), Mn3O4-MnO (MM), NiO-Ni (NNO), magnetite-wustite (MW), and iron-wustite (IW) buffers together with H2O. The nitrogen solubility ranges from about 1 to about 5 mol%, calculated as N, with ∂XN/∂P > 0 and ∂XN/∂fH2 > 0. The ∂/ ∂fH2(∂XN/∂P) is also positive. Raman and FTIR spectroscopic data are consistent with solution mechanisms that involve reduction of nitrogen with increasing fH2. At low fH2 [fH2(MH) and fH2(MM)], nitrogen is dissolved in melts only as molecular N2. At fH2(NNO) and fH2(MW), there is partial reduction of nitrogen to form N2, NH2 + complexes and molecular NH3 in the melts, whereas at the highest fH2(IW), only molecular NH3 and NH2- groups can be identified. OH groups are also formed whenever there is reduction of nitrogen from N2. Solution in silicate melts of reduced, NH-bearing species results in silicate melt depolymerization. At fH2(NNO) and fH2(MW), depolymerization occurs via H+ interaction with oxygen and NH2+ groups serving as network-modifier. Under more reducing conditions, oxygen is replaced by NH2- groups. Solution of reduced nitrogen in silicate melts causes depolymerization of their structure. This implies that melt properties that depend on silicate structure depend on redox conditions.

Original languageEnglish
Pages (from-to)1760-1770
Number of pages11
JournalAmerican Mineralogist
Volume93
Issue number11-12
DOIs
Publication statusPublished - Nov 2008

Fingerprint

Silicates
silicate melt
fugacity
Amines
Ferrosoferric Oxide
Hydrogen
silicates
amines
solubility
Nitrogen
Solubility
hydrogen
nitrogen
magnetite
depolymerization
Depolymerization
melt
Temperature
hematite
Bearings (structural)

Keywords

  • Melt
  • NOH volatiles
  • Spectroscopy
  • Structure

ASJC Scopus subject areas

  • Geochemistry and Petrology
  • Geophysics

Cite this

Solubility and solution mechanisms of NOH volatiles in silicate melts at high pressure and temperature - Amine groups and hydrogen fugacity. / Mysen, Bjorn O.; Yamashita, Shigeru; Chertkova, Nadezda.

In: American Mineralogist, Vol. 93, No. 11-12, 11.2008, p. 1760-1770.

Research output: Contribution to journalArticle

@article{eee4d2d1d58a449eba28583e2684c66e,
title = "Solubility and solution mechanisms of NOH volatiles in silicate melts at high pressure and temperature - Amine groups and hydrogen fugacity",
abstract = "The solubility and solution mechanisms of nitrogen in silicate melts have been examined via nitrogen analyses and vibrational spectroscopy (Raman and FTIR). Pressure (P), temperature (T), hydrogen fugacity (fH2), and silicate melt composition (degree of melt polymerization) were independent variables in experiments in the 1-2.5 GPa pressure and 1300-4500 °C temperature ranges. The fH2 was controlled at values defined by the magnetite-hematite (MH), Mn3O4-MnO (MM), NiO-Ni (NNO), magnetite-wustite (MW), and iron-wustite (IW) buffers together with H2O. The nitrogen solubility ranges from about 1 to about 5 mol{\%}, calculated as N, with ∂XN/∂P > 0 and ∂XN/∂fH2 > 0. The ∂/ ∂fH2(∂XN/∂P) is also positive. Raman and FTIR spectroscopic data are consistent with solution mechanisms that involve reduction of nitrogen with increasing fH2. At low fH2 [fH2(MH) and fH2(MM)], nitrogen is dissolved in melts only as molecular N2. At fH2(NNO) and fH2(MW), there is partial reduction of nitrogen to form N2, NH2 + complexes and molecular NH3 in the melts, whereas at the highest fH2(IW), only molecular NH3 and NH2- groups can be identified. OH groups are also formed whenever there is reduction of nitrogen from N2. Solution in silicate melts of reduced, NH-bearing species results in silicate melt depolymerization. At fH2(NNO) and fH2(MW), depolymerization occurs via H+ interaction with oxygen and NH2+ groups serving as network-modifier. Under more reducing conditions, oxygen is replaced by NH2- groups. Solution of reduced nitrogen in silicate melts causes depolymerization of their structure. This implies that melt properties that depend on silicate structure depend on redox conditions.",
keywords = "Melt, NOH volatiles, Spectroscopy, Structure",
author = "Mysen, {Bjorn O.} and Shigeru Yamashita and Nadezda Chertkova",
year = "2008",
month = "11",
doi = "10.2138/am.2008.2879",
language = "English",
volume = "93",
pages = "1760--1770",
journal = "American Mineralogist",
issn = "0003-004X",
publisher = "Mineralogical Society of America",
number = "11-12",

}

TY - JOUR

T1 - Solubility and solution mechanisms of NOH volatiles in silicate melts at high pressure and temperature - Amine groups and hydrogen fugacity

AU - Mysen, Bjorn O.

AU - Yamashita, Shigeru

AU - Chertkova, Nadezda

PY - 2008/11

Y1 - 2008/11

N2 - The solubility and solution mechanisms of nitrogen in silicate melts have been examined via nitrogen analyses and vibrational spectroscopy (Raman and FTIR). Pressure (P), temperature (T), hydrogen fugacity (fH2), and silicate melt composition (degree of melt polymerization) were independent variables in experiments in the 1-2.5 GPa pressure and 1300-4500 °C temperature ranges. The fH2 was controlled at values defined by the magnetite-hematite (MH), Mn3O4-MnO (MM), NiO-Ni (NNO), magnetite-wustite (MW), and iron-wustite (IW) buffers together with H2O. The nitrogen solubility ranges from about 1 to about 5 mol%, calculated as N, with ∂XN/∂P > 0 and ∂XN/∂fH2 > 0. The ∂/ ∂fH2(∂XN/∂P) is also positive. Raman and FTIR spectroscopic data are consistent with solution mechanisms that involve reduction of nitrogen with increasing fH2. At low fH2 [fH2(MH) and fH2(MM)], nitrogen is dissolved in melts only as molecular N2. At fH2(NNO) and fH2(MW), there is partial reduction of nitrogen to form N2, NH2 + complexes and molecular NH3 in the melts, whereas at the highest fH2(IW), only molecular NH3 and NH2- groups can be identified. OH groups are also formed whenever there is reduction of nitrogen from N2. Solution in silicate melts of reduced, NH-bearing species results in silicate melt depolymerization. At fH2(NNO) and fH2(MW), depolymerization occurs via H+ interaction with oxygen and NH2+ groups serving as network-modifier. Under more reducing conditions, oxygen is replaced by NH2- groups. Solution of reduced nitrogen in silicate melts causes depolymerization of their structure. This implies that melt properties that depend on silicate structure depend on redox conditions.

AB - The solubility and solution mechanisms of nitrogen in silicate melts have been examined via nitrogen analyses and vibrational spectroscopy (Raman and FTIR). Pressure (P), temperature (T), hydrogen fugacity (fH2), and silicate melt composition (degree of melt polymerization) were independent variables in experiments in the 1-2.5 GPa pressure and 1300-4500 °C temperature ranges. The fH2 was controlled at values defined by the magnetite-hematite (MH), Mn3O4-MnO (MM), NiO-Ni (NNO), magnetite-wustite (MW), and iron-wustite (IW) buffers together with H2O. The nitrogen solubility ranges from about 1 to about 5 mol%, calculated as N, with ∂XN/∂P > 0 and ∂XN/∂fH2 > 0. The ∂/ ∂fH2(∂XN/∂P) is also positive. Raman and FTIR spectroscopic data are consistent with solution mechanisms that involve reduction of nitrogen with increasing fH2. At low fH2 [fH2(MH) and fH2(MM)], nitrogen is dissolved in melts only as molecular N2. At fH2(NNO) and fH2(MW), there is partial reduction of nitrogen to form N2, NH2 + complexes and molecular NH3 in the melts, whereas at the highest fH2(IW), only molecular NH3 and NH2- groups can be identified. OH groups are also formed whenever there is reduction of nitrogen from N2. Solution in silicate melts of reduced, NH-bearing species results in silicate melt depolymerization. At fH2(NNO) and fH2(MW), depolymerization occurs via H+ interaction with oxygen and NH2+ groups serving as network-modifier. Under more reducing conditions, oxygen is replaced by NH2- groups. Solution of reduced nitrogen in silicate melts causes depolymerization of their structure. This implies that melt properties that depend on silicate structure depend on redox conditions.

KW - Melt

KW - NOH volatiles

KW - Spectroscopy

KW - Structure

UR - http://www.scopus.com/inward/record.url?scp=58049088365&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=58049088365&partnerID=8YFLogxK

U2 - 10.2138/am.2008.2879

DO - 10.2138/am.2008.2879

M3 - Article

VL - 93

SP - 1760

EP - 1770

JO - American Mineralogist

JF - American Mineralogist

SN - 0003-004X

IS - 11-12

ER -