A modeling of the structure and compressibility of quartz with a molecular potential and its transferability to cristobalite and coesite

Several computer models of quartz were developed and tested. A simple model based on a potential energy function, derived in large part from quantum mechanical calculations on the molecule H₆Si₂O₇, was found to reproduce the compressibility curve for quartz up to pressures of 8 GPa. The potential includes quadratic expressions for the SiO bond lengths, the OSiO angles and a parameter spanning the SiOSi angle together with an exponential OO repulsion term for non co-dimer O atoms. The variations in the cell edges and in the SiOSi angle, as a function of pressure, parallel observed trends when the bond lengths and angles calculated for the molecule are used as rgressor values. Poisson ratios calculated using the model match those observed. Two configurations for quartz related by the Dauphiné twin law are generated as minimum energy structures of the model with about equal frequencies as observed in nature. It is shown that the model, devised for quartz, can also be applied to the silica polymorph cristobalite, giving reasonable estimates of its compressibility curve, structural parameters and its negative Poisson ratio. When the observed bond lengths and angles are used as regressor values, the model generates the absolute coordinates of the atoms and the cell dimensions for quartz to within 0.005 Å and those of cristobalite to within 0.001 Å, on average, both at zero pressure. When applied to coesite, the model yields a zero pressure structure that is close to that observed but which is significantly softer than observed. The resulting SiO bond lengths are linearly correlated with f _s (O), as observed for coesite, despite the use of a single bond length and a single SiOSi angle as regressor values in the calculation. When the structures are optimized assuming P1 space group symmetry and triclinic cell dimensions, the resulting frameworks of silicate tetrahedra exhibit the translational, rotational and reflection symmetries observed for quartz, cristobalite and coesite. The fact that the resulting frameworks exhibit observed space group symmetries is evidence that the symmetry adopted by the silica polymorphs can be explained by short ranged forces.     

Bond length and radii variations in fluoride and oxide molecules and crystals

Molecular orbital calculations completed on fluoride molecules containing first and second row cations have generated bond lengths, R, that match those observed for coordinated polyhedra in crystals to within ～0.04 Å, on average. The calculated bond lengths and those observed for fluoride crystals can be ranked with the expression R=Kp ^?0.22, where p=s/r, s is the Pauling strength of the bond, r is the row number of the cation and K=1.34. The exponent -0.22 (≈ -2/9) is the same as that observed for oxide, nitride and sulfide molecules and crystals. Bonded radii for the fluoride anion, obtained from theoretical electron density maps, increase linearly with bond length. Those calculated for the cations as well as for the fluoride anion match calculated promolecule radii to within ～0.03 Å, on average, suggesting that the electron density distributions in the vicinity of the minima along the bond paths possess a significant atomic component despite bond type. Bonded radii for Si and O ions provided by experimental electron density maps measured for the oxides coesite, danburite and stishovite match those calculated for a series of monosilicic acid molecules. The resulting radii increase with bond length and coordination number with the radius of the oxide ion increasing at a faster rate than that of the Si cation. The oxide ion within danburite exhibits several distinct radii, ranging between 0.9 and 1.2 Å, rather than a single radius with each exhibiting a different radius along each of the nonequivalent bonds with B, Si and Ca. Promolecule radii calculated for the coordinated polyhedra in danburite match procrystal radii obtained in a structure analysis to within 0.002 Å. The close agreement between these two sets of radii and experimentally determined bonded radii lends credence to Slater's statement that the difference between the electron density distribution observed for a crystal and that calculated for a procrystal (IAM) model of the crystal “would be small and subtle, and very hard to determine by examination of the total charge density.”     

A Holocene record of climate change,fire ecology and human activity from montane Flat Top Bog,Maui

A sediment core from a high-elevation bog on Maui in the Hawaiian Islands contains evidence for drier conditions between 9.4–5.8 kyr BP, followed by a wetter interval between 5.8–2.2 kyr BP, and a variable late Holocene. These precipitation changes may be a reflection of vertical displacements of the upper boundary of the mid-Pacific Trade Wind Inversion (TWI) cloud layer. Fires, probably volcanically ignited, occurred in the forests prior to human arrival. Polynesian activity in this high-elevation, remote site was apparently limited, with no pollen, charcoal, or sedimentological evidence for local anthropogenic disturbance. After European contact, grass fires increased and introduced plant species invaded the site. Values for Cd, Cu, Pb, and Zn in sediments throughout the Holocene indicate low trace-metal deposition from atmospheric particulates at the site, even in the twentieth century.This paper is one of a series of papers guest edited by Dr. Mark Brenner on tropical paleolimnology     

Time-scale calibration by high-precision UPb zircon dating of interstratified volcanic ashes in the Ordovician and Lower Silurian stratotypes of Britain

High initial parent/daughter element ratios and a unique dual decay scheme make UPb zicron ages more precise and reliable than most isotopic ages, and thus inherently superior for time-scale calibration. Employing improved techniques to the conventional method of UPb dating, we have analyzed microgram-size (2–12 × 10⁻⁸ g) zircon fractions from biostratigraphically controlled volcanic ashes and dated key Paleozoic time-markers with a precision better than 1% (±2Ma). Four of the stratotype samples from Britain for which fission-track ages [1] were previously reported have yielded improved ages of:438.7 ± 2.0Ma for the lower Silurian zone of Coronograptus cyphus from Llandovery strata at Dob's Linn, southern Scotland;457.5 ± 2.2 Ma for a Middle Ordovician Caradoc (Longvillian) ash near Bala, North Wales, and;465.7 ± 2.1and464.6 ± 1.8 Ma for the Didymograptus artus Zone and the type Didymograptus Murchisoni Zone, respectively, of the Llanvirn Series at Arenig Fawr and Abereiddi Bay, Wales. Another sample from the zone of Dicellograptus anceps (P. pacificus Subzone) of the Ashgill Series at Dob's Linn has been dated at445.7 ± 2.4Ma, suggesting placement of the Ordovician-Silurian time boundary at approximately 441 Ma. A sixth bentonite from Caradocian age strata of North America (Spechts Ferry Shale, Decorah Formation, Missouri) is453.7 ± 1.8Ma old, indicating that the Rocklandian Stage of the Mohawkian Series is only slightly younger than the Longvillian Stage of the Caradoc Series in Britain.     

Rapid formation of large coastal sand bodies after emplacement of Magdalena river jetties,northern Colombia

The Magdalena River is noted for its high discharge of river sediment and its importance as the sediment source for a large delta complex and downdrift coastal sand bodies. The emplacement of jetties, completed in 1935 to stabilize the river mouth, contributed to major changes in the downstream coastal sand bodies. The western delta front retreated an average 65 m/yr. Puerto Colombia spit detached and migrated toward Puerto Colombia at rates of 230–430 m/yr, ultimately running into the town's quay and port facility. Galerazamba spit alternately elongated and shortened over the short term, leading to the destruction or damage of coastal town sites. Isla Cascajo acted as a significant sand trap with nearly 12 km² of accretion over a 47-year period. Sand is now bypassing the tombolo, and the accretion zone continues migrating southwest. The small Punta Canaos spit also has shown significant accretion since 1974. The changes imply high rates of sediment transport; furthermore their growth is probably dependent on jetty-caused alterations of wave patterns, causing remobilization of shelf sands as well as delta-derived sand.Understanding sand body evolution and behavior is important to future development of the northern Colombia coast. Placement of port facilities, recreational beaches, tourist villages, and related support facilities on these sand bodies, as well as utilizing the sand bodies for aggregate, beach nourishment sands for other areas, or heavy mineral resources will require significant planning.