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The thermodynamic mixing properties of the pyrope-grossular solid solution show large deviations from ideality, which could be partly related to Ca-Mg order/disorder. In this study, synthetic pyrope-grossular garnets with X_(Mg) = 1.00, 0.91, 0.75, 0.50, 0.24, 0.10, and 0.00 are observed using ^(17)O 3QMAS, ^(27)Al MAS, and ^(29)Si MAS NMR to examine Ca-Mg order/disorder behavior and crystal chemical variations. The ^(17)O 3QMAS NMR spectra show four distinct resonances, assigned to four different local oxygen coordination environments; two resemble end-member garnets (oxygen bonded to two Mg or two Ca) and two are intermediate (oxygen bonded to one Ca and one Mg), indicating that there are two distinct bond distances for the Mg-O and/or Ca-O bonds through the entire solid solution. Noticeable changes in the NMR peak position for two of the oxygen sites suggest that as X_(Mg) increases, the longer Ca-O bond shortens. The relative areas for the different oxygen sites are close to those predicted using a model of random Ca/Mg mixing. The maximum allowed reduction in configurational entropy from first neighbor Ca-Mg ordering is insignificant relative to other configurational entropy reductions and excess vibrational entropy. These conclusions are not inconsistent with published theoretical calculations suggesting some Ca-Mg ordering that involves correlations beyond the first neighbor, as suggested by published theoretical calculations. Even at 18.8 Tesla, the ^(27)Al MAS NMR spectra do not resolve different local Al sites with varying combinations of X cation neighbors. The ^(29)Si MAS NMR spectra have resonance broadening, probably caused by the addition of 0.15 wt% Fe_2O_3 in the synthetic samples, and are consistent with published results suggesting a small degree of Ca-Mg ordering that is not reflected in the ^(17)O NMR spectra.

The densities and viscosities of silicate melts depend strongly on pressure, in part because of potentially measurable structural rearrangements. In an attempt to further understand these changes and how they affect macroscopic properties, we have used 27Al MAS NMR to determine the coordination of the Al cations in a series of aluminosilicate glasses quenched from melts at pressures of 2 to 8 GPa, have measured the glass densities, and have applied an in-situ falling sphere method to measure melt viscosities at high pressure. Spectra from these four- and five-component glasses show increasing Al coordination with increasing pressure and with increasing average field strength of the modifier cation, as was previously reported for simpler compositions. These data also indicate that when multiple modifier cations are present (e.g., Ca and K), the Al coordination is lower than what would be expected from linear combinations of the appropriate aluminosilicate end-members. The viscosity of Ca3Al2Si6O18 melts, measured using a falling sphere method that combines multianvil techniques with synchrotron X-ray radiography, may reach a minimum at a pressure below 6 GPa. A quasi-thermodynamic approach using equilibrium constants for the reactions that generate high-coordinated Al suggests that this pressure may be related to a maximum in the concentration of five-coordinated Al. These results further support the concept that pressure-induced network structural transitions have direct implications for the macroscopic properties of high-pressure melts.

The 17 O NMR spectra of glasses quenched from melts at high pressure are often difficult to interpret due to overlapping peaks and lack of crystalline model compounds. High-pressure aluminosilicate glasses often contain significant amounts of [5] Al and [6] Al, thus these high-pressure glasses must contain oxygen bonded to high-coordinated aluminum. The 17 O NMR parameters for the minerals jadeite, pyrope, grossular, and mullite are presented to assist interpretation of glass spectra and to help test quantum chemical calculations. The 17 O NMR parameters for jadeite and grossular support previous peak assignments of oxygen bonded to Si and high-coordinated Al in high-pressure glasses as well as quantum chemical calculations. The oxygen tricluster in mullite is very similar to the previously observed tricluster in grossite (CaAl 4 O 7 ) and suspected triclusters in glasses. We also present 27 Al NMR spectra for pyrope, grossular, and mullite.

Aluminum is an important minor constituent of a number of high-pressure mantle silicates in which it substitutes for octahedrally coordinated silicon. In several cases, its solid solution may be linked to the presence of oxygen vacancies; in others, to charge balance with H + . Here we present new data from high-resolution, high-field (18.8 Tesla) 27 Al NMR of aluminous stishovite and of a non-stoichiometric perovskite with nominal composition MgSi 0.95 Al 0.05 O 2.975 . For the stishovite, we characterize the local structure of the symmetrical, octahedral site for Al. These results, combined with 27 Al{ 1 H} REDOR NMR, are consistent with hypothesized H + charge balance, although the presence of a significant fraction of randomly distributed oxygen vacancies could remain undetected. As in a recent previous study of a related perovskite composition, the observed ratio of Al at symmetrical octahedral B sites to that of Al at large, central A sites is about 2:1, indicating the presence of oxygen vacancies to account for charge neutrality in this phase. Such vacancies are not preferentially associated with the Al octahedra, however, suggesting a random distribution in the structure.

Disordering of Si and Al in natrolite, scolecite, mesolite, and gonnardite was investigated with 29 Si and 27 Al magic angle spinning nuclear magnetic resonance (MAS NMR) spectroscopy. The results indicate that with the exception of one sample of natrolite (from San Benito County, California), the natrolite, mesolite, and scolecite samples studied all exhibit small degrees ( 29 Si MAS NMR spectra and mathematical relations based on Al avoidance were used to calculate Si and Al occupancies across the tetrahedral sites in these minerals. Configurational entropies arising from Si-Al disorder in natrolite, mesolite, and scolecite can add an addition 1–2% [up to 11 J/(mol·K)] to the total entropies of these phases at 298.15 K, whereas it may add as much as 7% to that of gonnardite [up to 27.7 J/(mol·K)]. These results also concur with previous observations of a gap in Si-Al disordering between orthorhombic and tetragonal natrolite samples and suggest that the state of disorder in natrolite is a function of temperature. The 29 Si MAS NMR spectrum of gonnardite is consistent with a disordered natrolite framework structure, and not an intergrowth of thomsonite and natrolite structural domains.

Despite the importance of the chloride ion in magmas and the fluids that separate from them, very little is known about atomic-scale structural environments for Cl− in silicate glasses. We present here the first solid-state 35Cl NMR data for Cl in silicate and aluminosilicate glasses, made possible by the availability of very high (14.1 to 18.8 Tesla) magnetic fields. We find that 35Cl has a wide range in chemical shifts that correlate well with cation-Cl distance and thus contain considerable structural information. In general, Cl is coordinated primarily by network-modifying alkali or alkaline earth cations, and we see no evidence for Al-Cl bonding.