The distribution of sodium ions in aluminosilicate glasses: a high-field Na-23 MAS and 3Q MAS NMR study     

Sung Keun Lee  Jonathan F. Stebbins 《Geochimica et cosmochimica acta》2003,67(9):1699-1709

The local configurations around sodium ions in silicate glasses and melts and their distributions have strong implications for the dynamic and static properties of melts and thus may play important roles in magmatic processes. The quantification of distributions among charge-balancing cations, including Na⁺ in aluminosilicate glasses and melts, however, remains a difficult problem that is relevant to high-temperature geochemistry as well as glass science.Here, we explore the local environment around Na⁺ in charge-balanced aluminosilicate glasses (the NaAlO₂-SiO₂ join) and its distribution using ²³Na magic-angle spinning (MAS) nuclear magnetic resonance (NMR) spectroscopy at varying magnetic fields of 9.4, 14.1, and 18.8 T, as well as triple-quantum (3Q)MAS NMR spectroscopy at 9.4 T, to achieve better understanding of the extent of disorder around this cation. We quantify the extent of this disorder in terms of changes in Na-O distance (d[Na-O]) distributions with composition and present a structural model favoring a somewhat ordered Na distribution, called a “perturbed” Na distribution model. The peak position in ²³Na MAS spectra of aluminosilicate glasses moves toward lower frequencies with increasing Si/Al ratios, implying that the average d(Na-O) increases with increasing R. The peak width is significantly reduced at higher fields (14.1 and 18.8 T) because of the reduced effect of second-order quadrupolar interaction, and ²³Na MAS NMR spectra thus provide relatively directly the Na chemical shift distribution and changes in atomic environment with composition. Chemical shift distributions obtained from ²³Na 3Q MAS spectra are consistent with MAS NMR data, in which deshielding decreases with R. The average distances between Na and the three types of bridging oxygens (BOs) (Na-{Al-O-Al}, Na-{Si-O-Al}, and Na-{Si-O-Si}) were obtained from the correlation between d(Na-O) and isotropic chemical shift. The calculated d(Na-{Al-O-Al}) of 2.52 Å is shorter than the d(Na-{Si-O-Si}) of 2.81 Å, and d(Na-{Al-O-Al}) shows a much narrower distribution than the other types of BOs. ²³Na chemical shifts in binary (Al-free) sodium silicate glasses are more deshielded and have ranges distinct from those of aluminosilicate glasses, implying that d(Na-NBO) (nonbridging oxygen) is shorter than d(Na-BO) and that d(Na-{Si-O-Si}) in binary silicates can be shorter than that in aluminosilicate glasses. The results given here demonstrate that high-field ²³Na NMR is an effective probe of the Na⁺ environment, providing not only average structural information but also chemically and topologically distinct chemical shift ranges (distributions) and their variation with composition and their effects on static and dynamic properties.  相似文献   

Dissolution mechanisms of water in depolymerized silicate melts: Constraints from H and Si NMR spectroscopy and ab initio calculations     

Xianyu Xue  Masami Kanzaki 《Geochimica et cosmochimica acta》2004,68(24):5027-5057

Dissolution of water in magmas significantly affects phase relations and physical properties. To shed new light on the this issue, we have applied ¹H and ²⁹Si nuclear magnetic resonance (NMR) spectroscopic techniques to hydrous silicate glasses (quenched melts) in the CaO-MgO-SiO₂ (CMS), Na₂O-SiO₂, Na₂O-CaO-SiO₂ and Li₂O-SiO₂ systems. We have also carried out ab initio molecular orbital calculations on representative clusters to gain insight into the experimental results.The most prominent result is the identification of a major peak at ∼1.1 to 1.7 ppm in the ¹H MAS NMR spectra for all the hydrous CMS glasses. On the basis of experimental NMR data for crystalline phases and ab initio calculation results, this peak can be unambiguously attributed to (Ca,Mg)OH groups. Such OH groups, like free oxygens, are only linked to metal cations, but not part of the silicate network, and are thus referred to as free hydroxyls in the paper. This represents the first direct evidence for a substantial proportion (∼13∼29%) of the dissolved water as free hydroxyl groups in quenched hydrous silicate melts. We have found that free hydroxyls are favored by (1) more depolymerized melts and (2) network-modifying cations of higher field strength (Z/R²: Z: charge, R: cation-oxygen bond length) in the order Mg > Ca > Na. Their formation is expected to cause an increase in the melt polymerization, contrary to the effect of SiOH formation. The ²⁹Si MAS NMR results are consistent with such an interpretation. This water dissolution mechanism could be particularly important for ultramafic and mafic magmas.The ¹H MAS NMR spectra for glasses of all the studied compositions contain peaks in the 4 to 17 ppm region, attributable to SiOH of a range of strength of hydrogen bonding and molecular H₂O. The relative population of SiOH with strong hydrogen bonding grows with decreasing field strength of the network-modifying cations. Ab initio calculations confirmed that this trend largely reflects hydrogen bonding with nonbridging oxygens.  相似文献   

Solubility mechanisms of fluorine in peralkaline and meta-aluminous silicate glasses and in melts to magmatic temperatures     

Bjorn O. Mysen  George D. Cody 《Geochimica et cosmochimica acta》2004,68(12):2745-2769

Structural interaction between dissolved fluorine and silicate glass (25°C) and melt (to 1400°C) has been examined with ¹⁹F and ²⁹Si MAS NMR and with Raman spectroscopy in the system Na₂O-Al₂O₃-SiO₂ as a function of Al₂O₃ content. Approximately 3 mol.% F calculated as NaF dissolved in these glasses and melts. From ¹⁹F NMR spectroscopy, four different fluoride complexes were identified. These are (1) Na-F complexes (NF), (2) Na-Al-F complexes with Al in 4-fold coordination (NAF), (3) Na-Al-F complexes with Al in 6-fold coordination with F (CF), and (4) Al-F complexes with Al in 6-fold, and possibly also 4-fold coordination (TF). The latter three types of complexes may be linked to the aluminosilicate network via Al-O-Si bridges.The abundance of sodium fluoride complexes (NF) decreases with increasing Al/(Al + Si) of the glasses and melts. The NF complexes were not detected in meta-aluminosilicate glasses and melts. The NAF, CF, and TF complexes coexist in peralkaline and meta-aluminosilicate glasses and melts.From ²⁹Si-NMR spectra of glasses and Raman spectra of glasses and melts, the silicate structure of Al-free and Al-poor compositions becomes polymerized by dissolution of F because NF complexes scavenge network-modifying Na from the silicate. Solution of F in Al-rich peralkaline and meta-aluminous glasses and melts results in Al-F bonding and aluminosilicate depolymerization.Temperature (above that of the glass transition) affects the Qⁿ-speciation reaction in the melts, 2Q³ ⇔ Q⁴ + Q², in a manner similar to other alkali silicate and alkali aluminosilicate melts. Dissolved F at the concentration level used in this study does not affect the temperature-dependence of this speciation reaction.  相似文献   

Oxygen sites in hydrous aluminosilicate glasses: the role of Al-O-Al and H₂O     

Jane V OglesbyPeidong Zhao  Jonathan F Stebbins 《Geochimica et cosmochimica acta》2002,66(2):291-301

We describe here high-field ¹⁷O magic-angle-spinning (MAS) and triple-quantum MAS (3QMAS) NMR spectra for several alkali silicate and Na, K, and Ca aluminosilicate glasses containing up to 10 wt.% water. The H₂O site appears to have a large quadrupolar coupling constant, and its chemical shift increases from Na- to K- glasses, suggesting significant cation-H₂O interactions. In ¹⁷O one-pulse MAS and 3QMAS and ²⁷Al one-pulse NMR experiments, major differences were seen between spectra for anhydrous and hydrous calcium aluminosilicate glasses. The changes in the ¹⁷O MAS spectra can be explained by the addition of an H₂O peak and to the disappearance of an Al-O-Al peak from the ¹⁷O NMR spectrum for the hydrous glass. The ²⁷Al results are consistent with this interpretation.  相似文献   

Structure vs. composition: A solid-state H and Si NMR study of quenched glasses along the Na₂O-SiO₂-H₂O join     

George D. Cody  Bjorn O. Mysen 《Geochimica et cosmochimica acta》2005,69(9):2373-2384

A suite of six hydrous (7 wt.% H₂O) sodium silicate glasses spanning sodium octasilicate to sodium disilicate in composition were analyzed using ²⁹Si single pulse (SP) magic angle spinning (MAS) nuclear magnetic resonance (NMR) spectroscopy, ¹H-²⁹Si cross polarization (CP) MAS NMR, and fast MAS ¹H-NMR. From the ²⁹Si SPMAS data it is observed that at low sodium compositions dissolved water significantly depolymerizes the silicate network. At higher sodium contents, however, dissolved H₂O does not affect a significant increase in depolymerization over that predicted based on the Na/Si ratio alone. The fast MAS ¹H-NMR data reveal considerable complexity in proton environments in each of the glasses studied. The fast MAS ¹H-NMR spectra of the highest sodium concentration glasses do not exhibit evidence of signficantly greater fractions of dissolved water as molecular H₂O than the lower sodium concentration glasses requiring that the decrease in polymerization at high sodium contents involves a change in sodium solution mechanism. Variable contact time ¹H-²⁹Si cross polarization (CP) MAS NMR data reveal an increase in the rotating frame spin lattice relaxation rate constant (T_1ρ*) for various Qⁿ species with increasing sodium content that correlates with a reduction in the average ¹H-²⁹Si coupling strength. At the highest sodium concentration, however, T_1ρ* drops significantly, consistent with a change in the Na₂O solution mechanism.  相似文献   

Structure of hydrous aluminosilicate glasses along the diopside-anorthite join: A comprehensive one- and two-dimensional H and Al NMR study     

Xianyu Xue  Masami Kanzaki 《Geochimica et cosmochimica acta》2008,72(9):2331-2348

We have taken a systematic approach utilizing advanced solid-state NMR techniques to gain new insights into the controversial issue concerning the dissolution mechanisms of water in aluminosilicate melts (glasses). A series of quenched anhydrous and hydrous (∼2 wt% H₂O) glass samples along the diopside (Di, CaMgSi₂O₆)—anorthite (An, CaAl₂Si₂O₈) join with varying An components (0, 20, 38, 60, 80, and 100 mol %) have been studied. A variety of NMR techniques, including one-dimensional (1D) ¹H and ²⁷Al MAS NMR, and ²⁷Al → ¹H cross-polarization (CP) MAS NMR, as well as two-dimensional (2D) ¹H double-quantum (DQ) MAS NMR, ²⁷Al triple-quantum (3Q) MAS NMR, and ²⁷Al → ¹H heteronuclear correlation NMR (HETCOR) and 3QMAS/HETCOR NMR, have been applied. These data revealed the presence of SiOH, free OH ((Ca,Mg)OH) and AlOH species in the hydrous glasses, with the last mostly interconnected with Si and residing in the more polymerized parts of the structure. Thus, there are no fundamental differences in water dissolution mechanisms for Al-free and Al-bearing silicate melts (glasses), both involving two competing processes: the formation of SiOH/AlOH that is accompanied by the depolymerization of the network structure, and the formation of free OH that has an opposite effect. The latter is more important for depolymerized compositions corresponding to mafic and ultramafic magmas.Aluminum is dominantly present in four coordination (Al^IV), but a small amount of five-coordinate Al (Al^V) is also observed in all the anhydrous and hydrous glasses. Furthermore, six-coordinate Al (Al^VI) is also present in most of the hydrous glasses. As Al of higher coordinations are favored by high pressure, Al^VIOH and Al^VOH may become major water species at higher pressures corresponding to those of the Earth’s mantle.  相似文献   

Structure of Cl-containing silicate and aluminosilicate glasses: A Cl MAS-NMR study     

Travis O. Sandland  Jonathan F. Stebbins  James D. Webster 《Geochimica et cosmochimica acta》2004,68(24):5059-5069

Chlorine-35 magic angle spinning (MAS) nuclear magnetic resonance (NMR) spectra were collected at 14.1 and 18.8 Tesla fields to determine the atomic scale structural environments of the chloride ions in anhydrous and hydrous silicate and aluminosilicate glasses containing 0.2 to 0.7 wt% Cl. NMR peaks are broad and featureless, but are much narrower than the total chemical shift range for the nuclide in inorganic chlorides. Peak widths are primarily due to quadrupole interactions and to a lesser extent to chemical shift distributions. Peak positions are quite different for the Na- and Ca-containing glasses, suggesting that most Cl⁻ coordination environments contain network modifier cations. Comparison of peak positions and shapes for silicate and aluminosilicate glasses containing either Na or Ca suggests that there is no obvious contribution from Cl⁻ bonded to Al, and relative quantitation of peak areas indicates that there is no systematic undercounting of ³⁵Cl spins in the aluminous vs. the Al-free samples. In Ca-Na silicate glasses with varying Ca/(Ca + Na), the mixed-cation glasses have intermediate chemical shifts between those of the end members, implying that there is not a strong preference of either Ca²⁺ or of Na⁺ around Cl⁻. Hydrous Na-aluminosilicate glasses with H₂O contents up to 5.9 wt% show a shift to higher frequency NMR signal with increasing H₂O content, while the quadrupole coupling constant (C_Q) remains constant at ∼3.3 MHz. However, the change in frequency is much smaller than that expected if H₂O systematically replaced Na⁺ in the first-neighbor coordination shell around Cl⁻. A series of hydrous Ca-aluminosilicate glasses with H₂O contents up to 5.5 wt% show no shift in NMR signal with increasing H₂O content. The C_Q remains constant at ∼4.4 MHz, again suggesting no direct interaction between Cl⁻ and H₂O in these samples.  相似文献   

S-rich apatite-hosted glass inclusions in xenoliths from La Palma: constraints on the volatile partitioning in evolved alkaline magmas   总被引：3，自引：2，他引：1  

Fleurice Parat  François Holtz  Andreas Klügel 《Contributions to Mineralogy and Petrology》2011,162(3):463-478

The composition of S-rich apatite, of volatile-rich glass inclusions in apatite, and of interstitial glasses in alkaline xenoliths from the 1949 basanite eruption in La Palma has been investigated to constrain the partitioning of volatiles between apatite and alkali-rich melts. The xenoliths are interpreted as cumulates from alkaline La Palma magmas. Apatite contains up to 0.89 wt% SO₃ (3560 ppm S), 0.31 wt% Cl, and 0.66 wt% Ce₂O₃. Sulfur is incorporated in apatite via several independent exchange reactions involving (P⁵⁺, Ca²⁺) vs. (S⁶⁺, Si⁴⁺, Na⁺, and Ce³⁺). The concentration of halogens in phonolitic to trachytic glasses ranges from 0.15 to 0.44 wt% for Cl and from <0.07 to 0.65 wt% for F. The sulfur concentration in the glasses ranges from 0.06 to 0.23 wt% SO₃ (sulfate-saturated systems). The chlorine partition coefficients (D_Cl^{apatite/glass}) range from 0.4 to 1.3 (average D_Cl^{apatite/glass} = 0.8), in good agreement with the results of experimental data in mafic and rhyolitic system with low Cl concentrations. With increasing F in glass inclusions D_F^{apatite/glass} decreases from 35 to 3. However, most of our data display a high partition coefficient (~30) close to D_F^{apatite/glass} determined experimentally in felsic rock. D_S^{apatite/glass} decreases from 9.1 to 2.9 with increasing SO₃ in glass inclusions. The combination of natural and experimental data reveals that the S partition coefficient tends toward a value of 2 for high S content in the glass (>0.2 wt% SO₃). D_S^{apatite/glass} is only slightly dependent on the melt composition and can be expressed as: SO_{3 apatite} (wt%) = 0.157 * ln SO_{3 glass} (wt%) + 0.9834. The phonolitic compositions of glass inclusions in amphibole and haüyne are very similar to evolved melts erupted on La Palma. The lower sulfur content and the higher Cl content in the phonolitic melt compared to basaltic magmas erupted in La Palma suggest that during magma evolution the crystallization of haüyne and pyrrhotite probably buffered the sulfur content of the melt, whereas the evolution of Cl concentration reflects an incompatible behavior. Trachytic compositions similar to those of the (water-rich) glass inclusions analyzed in apatite and clinopyroxene are not found as erupted products. These compositions are interpreted to be formed by the reaction between water-rich phonolitic melt and peridotite wall-rock.  相似文献   

Solution mechanisms of H₂O in depolymerized peralkaline melts     

Bjorn O. Mysen  George D. Cody 《Geochimica et cosmochimica acta》2005,69(23):5557-5566

Solubility mechanisms of water in depolymerized silicate melts quenched from high temperature (1000°-1300°C) at high pressure (0.8-2.0 GPa) have been examined in peralkaline melts in the system Na₂O-SiO₂-H₂O with Raman and NMR spectroscopy. The Na/Si ratio of the melts ranged from 0.25 to 1. Water contents were varied from ∼3 mol% and ∼40 mol% (based on O = 1). Solution of water results in melt depolymerization where the rate of depolymerization with water content, ∂(NBO/Si)/∂X_H2O, decreases with increasing total water content. At low water contents, the influence of H₂O on the melt structure resembles that of adding alkali oxide. In water-rich melts, alkali oxides are more efficient melt depolymerizers than water. In highly polymerized melts, Si-OH bonds are formed by water reacting with bridging oxygen in Q⁴-species to form Q³ and Q² species. In less polymerized melts, Si-OH bonds are formed when bridging oxygen in Q³-species react with water to form Q²-species. In addition, the presence of Na-OH complexes is inferred. Their importance appears to increase with Na/Si. This apparent increase in importance of Na-OH complexes with increasing Na/Si (which causes increasing degree of depolymerization of the anhydrous silicate melt) suggests that water is a less efficient depolymerizer of silicate melts, the more depolymerized the melt. This conclusion is consistent with recently published ¹H and ²⁹Si MAS NMR and ¹H-²⁹Si cross polarization NMR data.  相似文献   

Sulfur K-edge XANES analysis of natural and synthetic basaltic glasses: Implications for S speciation and S content as function of oxygen fugacity   总被引：9，自引：0，他引：9  

Pedro J. Jugo  Max Wilke 《Geochimica et cosmochimica acta》2010,74(20):5926-7631

XANES analyses at the sulfur K-edge were used to determine the oxidation state of S species in natural and synthetic basaltic glasses and to constrain the fO₂ conditions for the transition from sulfide (S²⁻) to sulfate (S⁶⁺) in silicate melts. XANES spectra of basaltic samples from the Galapagos spreading center, the Juan de Fuca ridge and the Lau Basin showed a dominant broad peak at 2476.8 eV, similar to the spectra obtained from synthetic sulfide-saturated basalts and pyrrhotite. An additional sharp peak at 2469.8 eV, similar to that of crystalline sulfides, was present in synthetic glasses quenched from hydrous melts but absent in anhydrous glasses and may indicate differences in sulfide species with hydration or presence of minute sulfide inclusions exsolved during quenching. The XANES spectra of a basalt from the 1991 eruption of Mount Pinatubo, Philippines, and absarokitic basalts from the Cascades Range, Oregon, USA, showed a sharp peak at 2482.8 eV, characteristic of synthetic sulfate-saturated basaltic glasses and crystalline sulfate-bearing minerals such as hauyne. Basaltic samples from the Lamont Seamount, the early submarine phase of Kilauea volcano and the Loihi Seamount showed unequivocal evidence of the coexistence of S²⁻ and S⁶⁺ species, emphasizing the relevance of S⁶⁺ to these systems. XANES spectra of basaltic glasses synthesized in internally-heated pressure vessels and equilibrated at fO₂ ranging from FMQ − 1.4 to FMQ + 2.7 showed systematic changes in the features related to S²⁻ and S⁶⁺ with changes in fO₂. No significant features related to sulfite (S⁴⁺) species were observed. These results were used to construct a function that allows estimates of S⁶⁺/ΣS from XANES data. Comparison of S⁶⁺/ΣS data obtained by S Kα shifts measured with electron probe microanalysis (EPMA), S⁶⁺/ΣS obtained from XANES spectra, and theoretical considerations show that data obtained from EPMA measurements underestimate S⁶⁺/ΣS in samples that are sulfate-dominated (most likely because of photo-reduction effects during analysis) whereas S⁶⁺/ΣS from XANES provide a close match to the expected theoretical values. The XANES-derived relationship for S⁶⁺/ΣS as a function of fO₂ indicates that the transition from S²⁻ to S⁶⁻ with increasing fO₂ occurs over a narrower interval than what is predicted by the EPMA-derived relationship. The implications for natural systems is that small variation of fO₂ above FMQ + 1 will have a large effect on S behavior in basaltic systems, in particular regarding the amount of S that can be transported by basaltic melts before sulfide saturation can occur.  相似文献   

Sulfur diffusion in rhyolite melts     

L. L. Baker  Malcolm J. Rutherford 《Contributions to Mineralogy and Petrology》1996,123(4):335-344

 Diffusion rates for sulfur in rhyolite melt have been measured at temperatures of 800–1100° C, water contents of 0–7.3 wt%, and oxygen fugacities from the quartz-fayalite-magnetite buffer to air. Experiments involved dissolution of anhydrite or pyrrhotite into rhyolite melt over time scales of hours to days. Electron microprobe analysis was used to measure sulfur concentration profiles in the quenched glasses. Regression of the diffusion data in dry rhyolite melt gives D_sulfur=0.05·exp{−221±80RT}, which is one to two orders of magnitude slower than diffusion of other common magmatic volatiles such as H₂O, CO₂ and Cl^-. Diffusion of sulfur in melt with 7 wt% dissolved water is 1.5 to 2 orders of magnitude faster than diffusion in the anhydrous melt, depending on temperature. Sulfur is known to dissolve in silicate melts as at least two different species, S²⁻ and S⁶⁺, the proportions of which vary with oxygen fugacity; despite this, oxygen fugacity does not appear to affect sulfur diffusivity except under extremely oxidizing conditions. This result suggests that diffusion of sulfur is controlled by one species over a large range in oxygen fugacity. The most likely candidate for the diffusing species is the sulfide ion, S²⁻. Re-equilibration between S²⁻ and S⁶⁺ in oxidized melts must generally be slow compared to S²⁻ diffusion in order to explain the observed results. In a silicic melt undergoing degassing, sulfur will tend to be fractionated from other volatile species which diffuse more rapidly. This is consistent with analyses of tephra from the 1991 eruption of Mount Pinatubo, Philippines, and from other high-silica volcanic eruptions. Received: 26 April 1995 / Accepted: 1 November 1995  相似文献   

Water solubility mechanism in hydrous aluminosilicate glasses: information from Al MAS and MQMAS NMR     

D. Padro  B.C. Schmidt 《Geochimica et cosmochimica acta》2003,67(8):1543-1551

New ²⁷Al NMR data are presented in order to clarify the discrepancies in the interpretation of the previous ²⁷Al Magic Angle Spinning (MAS) spectra from hydrous aluminosilicate glasses. The ²⁷Al MAS data have been collected at much higher magnetic field (14.1 and 17.6 T) than hitherto, and in addition, multiple quantum (MQ) MAS NMR data are presented for dry and hydrous nepheline glasses and NaAlSi_7.7O_17.4 glass that, according to the model of Zeng et al. (Zeng Q., Nekvasil H., and Grey C. P. 2000. In support of a depolymerisation model for water in sodium aluminosilicate glasses: Information from NMR spectroscopy. Geochim. Cosmochim. Acta64, 883-896), should produce a high fraction (up to 30%) of Al in Al Q³-OH on hydration. Although small differences in the MAS spectra of anhydrous and hydrous nepheline glasses are observed, there is no evidence for the existence of significant (>∼2%) amounts of Q³ Al-OH in these glasses in either the MAS or MQMAS data.  相似文献   

Experimental data on the speciation of sulfur as a function of oxygen fugacity in basaltic melts   总被引：10，自引：0，他引：10  

Pedro J. Jugo  Robert W. Luth 《Geochimica et cosmochimica acta》2005,69(2):497-503

The speciation of sulfur as a function of oxygen fugacity was calculated in glasses of basaltic composition saturated experimentally with either sulfide or sulfate phases. The experiments were conducted on mixtures of synthetic and natural materials equilibrated at 1300 °C and 1 GPa in a piston-cylinder apparatus. Sulfur speciation was calculated by measuring the peak shift of the sulfur Kα radiation relative to a sulfide standard, whereas oxygen fugacity was calculated from the composition of olivine and spinel present in the assemblages. The results are consistent with sulfur being present as sulfite (S⁴⁺) in addition to sulfate (S⁶⁺) in oxidized melts. Therefore, sulfur speciation derived from SKα peak shifts should be seen as ”sulfate mole fraction equivalents“ (X(S⁶⁺)_eq.). Using the data available, an empiric function: