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.     

A study of the geoelectrical properties of peatlands and their influence on ground-penetrating radar surveying1

Geophysical surveys and chemical analyses on cores were carried out in three Ontario peatlands, from which we have gained a better understanding of the peat properties that control the geophysical responses. The electrical conductivity depends linearly on the concentration of total dissolved solids in the peat pore waters and the pore waters in turn bear the ionic signatures of the underlying mineral sediments. The ionic concentration, and thus the electrical conductivity, increase linearly from the surface to basement. The average bulk electrical conductivity of peatlands at Ellice Marsh, near Stratford, and at Wally Creek Area Forest Drainage Project, near Cochrane, are of the order of 25 mS/m. The Mer Bleue peatland, near Ottawa, has extremely high electrical conductivity, reaching levels of up to 380 mS/m near the base of the peat. The Mer Bleue peatland water has correspondingly high values of total dissolved solids, which originate from the underlying Champlain Sea glaciomarine clays. The dielectric permittivity in peats is largely controlled by the bulk water content. Ground penetrating radar can detect changes in water content greater than 3%, occurring within a depth interval less than 15 cm. The principal peatland interfaces detected are the near-surface aerobic to anaerobic transition and the peat to mineral basement contact. The potential for the successful detection of the basement contact using the radar can be predicted using the radar instrument specifications, estimates of the peatland depth, and either the bulk peat or the peat pore water electrical conductivities. Predicted depths of penetration of up to 10 m for Ellice Marsh and Wally Creek exceed the observed depths of 1 to 2 m. At Mer Bleue, on the other hand, we observe that, as predicted, a 100 MHz signal will penetrate to the base of a 2 m thick peat but a 200 MHz signal will not.     

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.”     

Seasonal variation of the stable isotopic compositions of coastal marine plankton from Woods Hole,Massachusetts and Georges Bank

A study of the isotopic composition of plankton from Woods Hole Harbor was conducted to investigate seasonal variation in carbon and nitrogen stable isotopes in a shallow coastal environment. Stable isotopic ratios of carbon and nitrogen both showed temporal variation on the scale of weeks to months, with heaviest (most positive) values in summer to fall for both isotopes. Particulate organic matter (POM) δ¹³C values were highest (?19‰ to ?21‰) in August to November and lower (?21‰ to ?25‰) at other times of the year, while δ¹³N-POM values were highest (9.5‰ to 12‰) in March to September and lower (7.5‰ to 9.5‰) at other times of the year. Stable isotopic values were significantly correlated with temperature, DI¹³C, and C∶N ratios, but not with [DIC], [POC], [PN], [chlorophyll], or the taxonomic composition of the phytoplankton. There was no direct evidence of allochthonous inputs of carbon and nitrogen to the system. Woods Hole δ¹³C values were virtually identical to Georges Bank plankton values; similar POC: Chlorophyll and C∶N ratios in the two systems further suggest that Woods Hole Harbor is principally a marine system. The high δ¹³C values of net plankton (>20 μm) during summer and early fall are consistent with a smaller degree of photosynthetic isotopic fractionation at that time, related to temperature and/or [CO_2(aq)]. This pattern was not seen, however, in total POM. Plankton δ¹³N values were higher in Woods Hole Harbor than on Georges Bank, especially during warmer periods, possibly due to high rates of nitrification and organic matter recycling in Woods Hole waters. Relatively wide ranges of stable isotopic values from both Woods Hole Harbor and Georges Bank suggest that seasonality should be considered when attempting to establish endmember C and N isotopic values for temperate marine plankton. Preliminary results from size-fractionated samples suggest that cyanobacteria may fractionate carbon isotopes to a greater degree than net phytoplankton.     

Diver-operated piston corer for nearshore use

A diver-operated piston corer suitable for collecting cores of >3 m length from fine-grained nearshore sediment has been developed. The corer uses a platform that rests on the sediment surface supporting both the operators and a derrick that maintains the piston at the sediment-water interface. The core is insected into and recovered from the sediment manually. The technique offers several advantages; low cost, minimal disruption of the sediment-water interface, little compaction of the sediment, the ability to collect longer length cores than is possible with gravity corers, and the ability to be deployed from relatively small boats. Dissolved ammonium and inorganic carbon data are presented from a 3.3-m core collected by this technique from Tomales Bay, California.     

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