Cation disorder in garnets along the Mg3Al2Si3O12-Mg4Si4O12 join: an infrared,Raman and NMR study     

Paul McMillan  Masaki Akaogi  Eiji Ohtani  Quentin Williams  Ronald Nieman  Robert Sato 《Physics and Chemistry of Minerals》1989,16(5):428-435

We have obtained infrared and Raman spectra for garnets synthesized at high (static) pressures and temperatures along the join Mg₃Al₂Si₃O₁₂ (pyrope) — Mg₄Si₄O₁₂ (magnesium majorite). The vibrational spectra of Mg-majorite show a large number of additional weak peaks compared with the spectra of cubic pyrope garnet, consistent with tetragonal symmetry for the MgSiO₃ garnet phase. The Raman bands for this phase show no evidence for line broadening, suggesting that Mg and Si are ordered on octahedral sites in the garnet. The bands for the intermediate garnet compositions are significantly broadened compared with the end-members pyrope and Mg-majorite, indicating cation disorder in the intermediate phases. Solid state ²⁷Al NMR spectroscopy for pyrope and two intermediate compositions show that Al is present only on octahedral sites, so the cation disorder is most likely confined to Mg-Al-Si mixing on the octahedral sites. We have also obtained a Raman spectrum for a natural, shock-produced (Fe,Mg) majorite garnet. The sharp Raman peaks suggest little or no cation disorder in this sample.  相似文献   

Raman spectroscopic studies of carbonates part I: High-pressure and high-temperature behaviour of calcite,magnesite, dolomite and aragonite     

Philippe Gillet  Claudine Biellmann  Bruno Reynard  Paul McMillan 《Physics and Chemistry of Minerals》1993,20(1):1-18

The room-temperature Raman spectra of aragonite, magnesite and dolomite have been recorded up to 30 GPa and 25 GPa, respectively and no phase changes were observed during compression, unlike calcite. The effect of temperature on the room-pressure Raman spectra of calcite, aragonite, magnesite and dolomite is reported up to 800–1100 K. The measured relative pressure and temperature-shifts of the Raman lines are greater for the lattice modes than for the internal modes of the CO₃ groups. These shifts are used to calculate the mode anharmonic parameters of the observed Raman modes; they are negative and their absolute values are smaller (close to 0) for the internal CO₃ modes than for the lattice modes (4–17 10^?5 K^?1). The temperature shifts of the lattice modes in calcite are considerably larger than those for dolomite and magnesite, and a marked non-linear increase in linewidth is observed above 400° C for calcite. This is consistent with an increasing relaxational component to the libration of the CO₃ groups about their threefold axes, premonitory to the rotational order-disorder transition at higher temperature. This behaviour is not observed for the other calcite structured minerals in this study. We examine systematic variations in the lattice mode frequencies and linewidths with composition, to begin to understand these differences in their anharmonic behaviour. Finally, we have used a simple Debye-Waller model to calculate atomic displacements in calcite, magnesite and dolomite with increasing temperature from the vibrational frequency data, to provide a direct comparison with atomic positional data from high-temperature structure refinements.  相似文献   

A Raman spectroscopic study of H/D isotopically substituted hydrous aluminosilicate glasses     

Paul F. McMillan  Brent T. Poe  Thomas R. Stanton  Richard L. Remmele 《Physics and Chemistry of Minerals》1993,19(7):454-459

We have obtained high quality Raman spectra for two H/D isotopically substituted hydrous aluminosilicate glasses with compositions along the NaAlSi₃O₈-SiO₂ join. Consistent with the results of previous studies, the isotope shift for the band near 900 cm^–1, whose intensity grows with increasing water content, is extremely small: v _h /v _d = 1.004 ± 0.004. The lack of a definite H/D isotope shift for this band does not, however, preclude its association with a vibration of a hydrous species in the glass, because of likely strong coupling between different vibrational modes of hydrated framework species. The 900 cm^–1 band could well be due to a T — OH (T = Si, Al) stretching or bending vibration in the hydrous glass, as required by the presence of a combination band near 4500 cm^–1 in near-infrared spectra.  相似文献   

Comparison of intertidal habitat use and growth rates of two northern Puget Sound cohorts of 0+ age Dungeness crab,Cancer magister     

Russell O. McMillan  David A. Armstrong  Paul A. Dinnel 《Estuaries and Coasts》1995,18(2):390-398

Density, habitat use, and growth of intertidal 0+ age Dungeness crabs, Cancer magister, were examined at five northern Puget Sound (Washington, USA) sites between June 1984 and September 1987. Sampling was conducted biweekly during settlement, from June to September, and approximately monthly or bimonthly thereafter. Northern Puget Sound Dungeness crab populations appear to be largely supported by recruitment from inland parental stocks, but a smaller proportion of recruits originate from coastal or oceanic stocks, as evidenced by earlier settlement and larger size of the first instar. Settlement of Dungeness crabs in inland waters typically peaked in August, and interannual variation in year-class strength at settlement (measured as intertidal density) was low relative to that reported for coastal crab populations. Spatial and interannual differences in settlement densities were mediated by high postsettlement mortality, which varied inversely with habitat complexity. Seasonal densities were highest in mixed sand and gravel with an overstory of attached or drift macroalgae, intermediate in eelgrass (Zostera marina), and lowest on open sand. Postsettlement growth rates corresponded to seasonal water temperatures and were greatest for the coastal cohort that settled in May and June. This cohort was larger as first juvenile instars (7.2 mm carapace width, CW) and grew rapidly at summer temperatures in excess of 15°C to a size (>30 mm CW) that allowed emigration from intertidal to subtidal areas by September. The late summer cohort settled in August at 5.3 mm CW and soon after was subjected to decreasing autumn water temperatures. There crabs experienced little growth while over wintering in the intertidal, but growth rates increased in March, and the crabs emigrated in April and May, approximately 10 mo after settlement.  相似文献