Thermoelastic properties of minerals

The simple theory of equation of state recently developed by Kumar is used to investigate the temperature and pressure dependence of elastic moduli of MgO. The results are found to present good agreement with the experimental data. It is concluded that the Kumar formulation is far better than the Suzuki theory of thermal expansivity, and the Shanker formulation is not a new relation.     

Multiple stages of phengite formation in Sanbagawa schists

Summary Basic and pelitic schists of the garnet and biotite zones in the Sanbagawa belt in Shikoku, Japan, commonly contain phengite developed at different stages of metamorphism. Textures of the phengite and associated minerals show that Al-rich phengite is a prograde product and Al-poor phengite is a retrograde product.

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Mehrfache Stadien der Phengit-Bildung in den Sanbagawa-Schiefern

Zusammenfassung Basische und pelitische Schiefer der Granat- und Biotitzonen im Sanbagawa Gürtel in Shikoku, Japan, führen Phengite, die während verschiedener Stadien der Metamorphose entstanden sind. Texturen der Phengite und assoziierter Minerale zeigen, daß Al-reicher Phengit das Produkt prograder Metamorphose ist, während Al-armer Phengit auf retrograde Metamorphose zurückgeht.

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With 5 Figures

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On leave from the Geological Survey of Slovakia, Spissa, Spisska, Nova Ves, Slovakia     

Transient loading-related settlement of a square foundation on geogrid-reinforced sand

Summary Laboratory model test results are presented that determine the effectiveness of using layers of geogrids as reinforcement in sand to reduce the settlement of square surface foundations subjected to transient loading. The model tests were conducted with only one type of geogrid at one relative density of compaction of sand. The maximum intensity of the transient load applied always exceeded the static ultimate bearing capacity of the foundation when supported by unreinforced sand. The settlement reduction factors for various depths of reinforcement have been determined.     

Fluid inclusion and cathodoluminescence studies on fluorite from the Kerio valley, Kenya

The Kerio valley lies between the Elgeyo escarpment and the Tugen hills which mark the western margin of the Kenya rift valley. The main fluorite deposits are located in the southern part of the valley at Kimwarer, Choff and Kamnaon.Three types of inclusion fillings were identified: Liquid+Vapour, Liquid+Daughter Minerals and Liquid. The L+V type is dominant. Inclusions occur as clusters, trails along the crystal growth zones and as isolated ones. Low salinities, apparently lower than the 5% wt. NaCl equivalent, were established. Homogenization temperatures suggest that fluorite mineralization took place at different stages and at temperatures between 120 and 180 °C. Isolated readings above 180°C may be referring to the original inclusions in limestone. These measurements and the absence of CO₂ in the inclusions, as well as the occurrence of vugs and crustifications with fluorite, suggest that mineralization took place at relatively shallow depths.Emission spectrum lines representing Eu²⁺, Dy³⁺, Tb³⁺ and Sm³⁺ in fluorite were identified. Sm³⁺ was detected only in the pinkish luminescence of veined fluorite, whereas the pinkish zone in banded fluorite contains Tb³⁺. Eu²⁺ which gives the strongest emission lines in the blue part of the visible spectrum, apparently is responsible for the strong blue cathodoluminescence (CL) in fluorite. The dominance of Eu²⁺ peaks further points to the fact that fluorite mineralization in the Kerio valley took place in an environment that was enriched in Lanthanide Rare Earth Elements (LREE). The presence of rare earths and radioactive elements in fluorite points towards their enrichment in the environment of fluorite mineralization. A juvenile origin of mineral forming solutions is proposed.Two generations of fluorite were established: allotriomorphic fluorite, forming the matrix, and the idiomorphic variety, occurring either in barite or in druzes in early fluorite. Barite in turn forms idiomorphic crystals in allotriomorphic fluorite. Relics of calcite occur in both K-feldspars and in early fluorite. Oxides and hydroxides of Fe, Mn, Ti and Al commonly occur in open spaces in fluorite. Of significance is the presence of gold in fluorite. Fluorite mineralization is of hydrothermal origin in the post-Miocene era and was formed as a result of metasomatic replacement of marble and open space fillings.     

Correlation of spectroscopic properties and substitutional sites of Cr3+ in aluminosilicates: II. Andalusite and sillimanite

This paper is an extension of the earlier one dealing with kyanite in which the best fitting value of the oxygen ligand distance for Cr³⁺ is adopted to study the spectroscopic properties of Cr³⁺ ions doped at the two possible Al sites in the other two polymorphs of the aluminosilicate group (Al₂O₃ · SiO₂), namely, andalusite and sillimanite. The superposition model and the crystal field analysis package recently developed for 3d ions doped at arbitrary low symmetry sites in crystals are used to predict energy levels and statevectors within the whole 3d ³ configuration. Then the values of the ground state zerofield splitting for Cr³⁺ ions at each Al sites in the two crystals are obtained. The splittings of the lower excited states ² E and ⁴ T ₂ as well as the admixture of ⁴ T ₂ into ² E have also been predicted. Comparison of our results with the available experimental data enable us to correlate the optical and EPR Spectroscopic properties with the substitutional Cr³⁺ sites. The conclusion is that in andalusite and sillimanite only the Al sites with nearly-octahedral six-fold coordination seem to be occupied by Cr³⁺ ions.     

Co2+ in trigonal fields of oxygen based structures: Electronic absorption spectra of buetschliite-type K2Co(SeO3)2, K2Co2(SeO3)3 and zemannite-type K2Co2(SeO3)3 · 2H2O

Polarized single crystal absorption spectra, in the spectral range 40 000–5 000 cm^-1, were obtained on Co²⁺ in trigonally distorted octahedral oxygen fields of buetschliite-type K₂Co(SeO₃)₂ (I), K₂Co₂(SeO₃)₃ (II) and zemannite-type K₂Co₂(SeO₃)₃ · 2H₂O (III). Site symmetries of Co²⁺ are m (D_3d) in I, 3m (C_3v) in II, and 3 (C₃) in III. The spectra can be interpreted on the basis of an electric dipole mechanism, wherein transitions of Co²⁺ in the centrosymmetric site in I gain intensity from dynamic removal of the inversion centre by vibronic coupling. In accordance with the elongation of the CoO₆ octahedra along the trigonal axis, the split component E_(g) of the ground state ⁴T_1g in octahedral fields is the ground state in all three compounds. Trigonal field parameters Dq_(trig), D, D and the Racah parameters B have been fitted to the energies of spin allowed transitions (293 K) as follows: I: 744, 94, -16, and 838 cm^-1, resp.; II: 647, 227, 42, and 798 cm^-1, resp.; III: 667, 181, 21, and 809 cm^-1, respectively. Racah parameters C were estimated from the energy of some observed spin-forbidden transitions to be 3770 (I), 3280 (II), and 3465 cm^-1 (III). Values of Dq and of the Racah parameters B and C indicate slight differences of Co²⁺-O bonding in I as compared to II and III, with somewhat higher covalency in compounds II and III which contain face-sharing CoO₆ octahedra with short Co-Co contacts. Also, in II and III the observed D values do not agree with theoretical D values, predicted from the magnitude of the mean octahedral distortions.     

Calibration of Al/Si order variations in anorthite

New single crystal diffraction data for natural and heat-treated anorthite crystals (Angel et al. 1990) allow the determination of their states of Al/Si order in terms of a macroscopic order parameter,Q _OD , for the transition. Numerical values ofQ _OD obtained from estimates of site occupancies are shown to vary with the scalar spontaneous strain, _s , as _s Q _OD ² , and with the ratio of the sums of typeb (superlattice) reflections and typea (sublattice) reflections asI _b/I _a Q _OD ² . An empirical calibration for pure anorthite is obtained giving varies between 0.92 and 0.87 in samples equilibrated at T1300° C, but then falls off relatively rapidly with increasing temperature, reaching 0.7 near the melting point ( 1557° C). The observed temperature dependence does not conform to the predictions of the simplest single order parameter models; coupling ofQ _OD withQ of the transition is suspeeted.     

Nourishment of perched sand dunes and the issue of erosion control in the Great Lakes

Although limited in coverage, perched sand dunes situated on high coastal bluffs are considered the most prized of Great Lakes dunes. Grand Sable Dunes on Lake Superior and Sleeping Bear Dunes on Lake Michigan are featured attractions of national lakeshores under National Park Service management. The source of sand for perched dunes is the high bluff along their lakeward edge. As onshore wind crosses the bluff, flow is accelerated upslope, resulting in greatly elevated levels of wind stress over the slope brow. On barren, sandy bluffs, wind erosion is concentrated in the brow zone, and for the Grand Sable Bluff, it averaged 1 m³/yr per linear meter along the highest sections for the period 1973–1983. This mechanism accounts for about 6,500 m³ of sand nourishment to the dunefield annually and clearly has been the predominant mechanism for the long-term development of the dunefield. However, wind erosion and dune nourishment are possible only where the bluff is denuded of plant cover by mass movements and related processes induced by wave erosion. In the Great Lakes, wave erosion and bluff retreat vary with lake levels; the nourishment of perched dunes is favored by high levels. Lake levels have been relatively high for the past 50 years, and shore erosion has become a major environmental issue leading property owners and politicians to support lake-level regulation. Trimming high water levels could reduce geomorphic activity on high bluffs and affect dune nourishment rates. Locally, nourishment also may be influenced by sediment accumulation associated with harbor protection facilities and by planting programs aimed at stabilizing dunes.     

Comparative compressibilities of majorite-type garnets

Relative compressibilities of five silicate garnets were determined by single-crystal x-ray diffraction on crystals grouped in the same high-pressure mount. The specimens include a natural pyrope [(Mg_2.84Fe_0.10Ca_0,06) Al₂Si₃O₁₂], and four synthetic specimens with octahedrally-coordinated silicon: majorite [Mg₃(MgSi)Si₃O₁₂], calcium-bearing majorite [(Ca_0.49Mg_2.51)(MgSi)Si₃0₁₂], sodium majorite [(Na_1.88Mgp_0.12)(Mg_0.06Si_1.94)Si₃O₁₂], and an intermediate composition [(Na_0.37Mg_2.48)(Mg_0.13Al_1.07 Si₀₈₀) Si₃O₁₂]. Small differences in the compressibilities of these crystals are revealed because they are subjected simultaneously to the same pressure. Bulk-moduli of the garnets range from 164.8 ± 2.3 GPa for calcium majorite to 191.5 ± 2.5 GPa for sodium majorite, assuming K′=4. Two factors, molar volume and octahedral cation valence, appear to control garnet compression.     

Nutrient enrichments and phytoplankton growth in the surface waters of the Louisiana Bight

Nitrate concentrations have increased twofold in the Mississippi River during the past three decades. The increased nitrogen loading to the Louisiana shelf has been postulated as a factor leading to eutrophication and the subsequent development of hypoxia west of the Mississippi River delta. While ratios of nitrogen:phosphorus and nitrogen:silica are relatively high in surface waters on the western Louisiana shelf, nitrogen has been posed as the ‘limiting’ nutrient in this region. Bioassays were performed with nutrient additions to surface waters collected from the Louisiana shelf to examine the potential for specific nutrient limitation. Experiments were conducted in March and September 1991, and May 1992. The growth responses of natural and cultured phytoplankton populations were determined by measuring the time course of in vivo and 3-(3,4 dichlorophenyl)-1, 1-dimethylurea (DCMU)-induced fluorescence, as well as initial and final chlorophylla concentrations. The results suggest that phosphate and silicate potentially limit phytoplankton growth during the winter-spring, particularly at low salinities. In late summer, in contrast, nitrogen limitation may be prominent at higher salinities.