Sapphirine II

The crystal structure of aP2₁/a polymorph of sapphirine (a=11.286(3),b=14.438(2),c=9.957(2) Å, β=125.4(2) °) of composition [Mg_3.7Fe _0.1 ²⁺ Al_4.1- Fe _0.1 ³⁺ ]^IV[Si_1.8Al_4.2]^IVO₂₀ was refined using structure factors determined by both neutron and x-ray diffraction methods to conventionalR factors of 0.067 and 0.031. respectively, forF _obs>2σ. The results of the two refinements agree reasonably well, but a half-normal probability plot (Abrahams, 1974) comparing the two data sets indicates that the pooled standard deviations of the atomic coordinates have been underestimated by a factor of two. The structure of sapphirine, solved initially by Moore (1969), consists of cubic closest packed oxygens with octahedral and predominantly tetrahedral layers alternately stacked along [100]. The layer in which 70% of the octahedral sites are occupied has an Mg-Al distribution characterized by Mg-rich octahedra sharing edges mainly with Al-rich octahedra. Mean octahedral bond lengths correlate well with Al occupancy determined by neutron site refinement if the relative number of shared octahedral edges is taken into account (see Table 1). The predominantly tetrahedral layer has 10% of the octahedral sites occupied by Al and 30% of the tetrahedral sites occupied by Al-Si in the ratio 2.33∶1. There are single chains of Al-Si tetrahedra parallel toz with corner-sharing wing tetrahedra (T5 andT6) on either side in the (100) plane. The meanT-O distance is highly correlated with Al occupancy, X_Al, as determined from the neutron site refinement: $$\langle T - O\rangle = 1.656 + 0.105X_{Al} (r^2 = 0.995).$$ Details of the neutron refinement are summarized below.     

A test of two alteration indices as predictors of argon loss in basic rocks

It has been proposed that the degree of alteration of basic rocks, as quantified by alteration indices based on H₂O⁺ contents or X-ray diffraction methods, can be used as a predictor of Ar loss. These hypotheses were tested using a sample of 36 zeolite facies metavolcanic basic rocks from Skye, Scotland, U.K., and found to be wanting. Hence, no independent criteria of Ar loss can be determined using these indicators.     

The petrogenesis of an I-type volcanic-plutonic suite: The St. Marys Porphyrite,Tasmania

The Devonian I-type St. Marys Porphyrite (388±1Ma) comprises two petrographically similar units, an 800 m thick pyroclastic sheet (compositionally dacite and rhyolite) and a subvolcanic feeder dyke. The pyroclastics are crystal-rich and contain (in order of decreasing abundance) plagioclase, quartz, biotite, augite, hypersthene and sanidine phenocrysts in an aphanitic groundmass.The early phenocryst assemblage clinopyroxene+orthopyroxene+plagioclase was followed by crystallisation of less magnesian pyroxene, more sodic plagioclase and biotite, quartz and K-feldspar. The phenocrysts crystallised at high temperature, between 1,000°-850° C, and at a pressure of 2.5±1 kb from a water undersaturated (<2.5 wt.%) magma in a chamber underlying the intrusive centre.At least two eruptive phases are present in the pyroclastic pile, each commencing with rhyolite. Bulk chemical variation probably reflects a zonation in the magma chamber prior to eruption. The low pressure phenocryst crystallisation conditions and the pyroxene Fe-enrichment trend with falling temperature support a fractional crystallisation model. The chemical variation can be explained by 20% fractional crystallisation involving plagioclase, quartz, biotite and pyroxene in proportions similar to modal phenocryst abundances.Volcanics like the St. Marys Porphyrite preserve evidence of their early magmatic history by quenching of mineral phases. Textural relationships and physico-chemical parameters deduced from the St. Marys Porphyrite are applicable to the interpretation of I-type granitoids in eastern Australia and elsewhere and constrain petrogenetic models for their genesis. Pyroxene cores of hornblende grains, pyroxene inclusions in plagioclase and corroded cores of plagioclase crystals may be formed through magmatic crystallisation and need not represent restite.     

A compact representation of ocean wave directionality

The spectrum of the longshore component of shoreward directed momentum flux ($\text{S}{}_{\mathrm{xy}}$) due to ocean waves, taken with the energy spectrum for the same wave field, is shown to provide a compact and useful representation of ocean wave directionality. Records of orthogonal surface slope components are demonstrated to yield an unbiased estimate of $\text{S}{}_{\mathrm{xy}}$. One method for estimation of $\text{S}{}_{\mathrm{xy}}$ using this relationship is investigated. Error analysis provides means for optimal selection of measurement parameters. Experimental verification is provided from laboratory tests and from field comparison with a five-element linear array.     

Intermediate degree p-mode frequency splittings near solar maximum

We report on observations of global solar Ca K-line intensity oscillations taken in May 1991 from Mees Solar Observatory, Hawaii. We measurep-mode frequency splittings for modes of spherical harmonic degrees between 20 and 129 averaged over the radial order of the modes. Our measurement of the antisymmetric component of the splittings is comparable with previous measurements and thus indicates a decrease in the latitudinal differential rotation with depth into the convection zone and the upper radiative zone. We find evidence for a 1% variation in the rotation rate of the upper convection zone roughly in phase with the solar activity cycle. Our measurement of the symmetric component of the splittings is of the same order as was reported from the previous solar maximum and is an order of magnitude larger than has been measured near solar minimum. From the degree dependence of the symmetric component of the splittings, we find evidence for an aspherical fractional sound speed perturbation located at a depth of 0.85 ± 0.05 solar radii. This perturbation has a magnitude ofc/c +9 × 10^–4 at the equator relative to the poles. Additionally, there is evidence for a near-surface aspherical sound speed perturbation of smaller magnitudec/c +4 × 10^–4 at the equator relative to the poles. If an intense global magnetic field were the dominant source of the observed symmetric component of the splittings, instead of latitudinal gradients in the sound speed, then global fields of order 10⁵ G would be required in the convection zone.     

A Simple Model for the Afternoon and Early Evening Decay of Convective Turbulence Over Different Land Surfaces

A simple model to study the decay of turbulent kinetic energy (TKE) in the convective surface layer is presented. In this model, the TKE is dependent upon two terms, the turbulent dissipation rate and the surface buoyancy fluctuations. The time evolution of the surface sensible heat flux is modelled based on fitting functions of actual measurements from the LITFASS-2003 field campaign. These fitting functions carry an amplitude and a time scale. With this approach, the sensible heat flux can be estimated without having to solve the entire surface energy balance. The period of interest covers two characteristic transition sub-periods involved in the decay of convective boundary-layer turbulence. The first sub-period is the afternoon transition, when the sensible heat flux starts to decrease in response to the reduction in solar radiation. It is typically associated with a decay rate of TKE of approximately t ⁻² (t is time following the start of the decay) after several convective eddy turnover times. The early evening transition is the second sub-period, typically just before sunset when the surface sensible heat flux becomes negative. This sub-period is characterized by an abrupt decay in TKE associated with the rapid collapse of turbulence. Overall, the results presented show a significant improvement of the modelled TKE decay when compared to the often applied assumption of a sensible heat flux decreasing instantaneously or with a very short forcing time scale. In addition, for atmospheric modelling studies, it is suggested that the afternoon and early evening decay of sensible heat flux be modelled as a complementary error function.     

The structure of hematite (α-Fe2O3) (001) surfaces in aqueous media: scanning tunneling microscopy and resonant tunneling calculations of coexisting O and Fe terminations

The iron oxide-water interface is of interest not only in geochemical and environmental processes, but also in fields ranging from corrosion to photocatalysis. The structure of α-Fe₂O₃ (001) surfaces is not fully understood, and questions have arisen recently concerning different terminations of (001) terraces; a so-called Fe-termination is expected, but under some conditions an O-termination may also be possible. Ultra-high vacuum (UHV) scanning tunneling microscope (STM) studies report evidence for an O-termination in coexistence with an Fe-termination, but other studies find no evidence for an O-termination. Molecular mechanics studies suggest that an O-termination should be possible in an aqueous environment. An O-termination could result from dissolution; if Fe atoms were to dissolve from an Fe-termination, an O-termination would presumably result (and vice-versa). We imaged hematite (001) surfaces in air and aqueous solution using STM. To aid interpretation of the images, we use a resonant tunneling model (RTM) parameterized using ab initio calculations.Our STM and RTM results are consistent with mixed O- and Fe-terminated (001) surfaces. For acid-etched surfaces we find evidence for a periodic (with wavelength of 2.2 ± 0.2 nm) arrangement of nominal O- and Fe-terminated domains. Two different borders between domains should occur, one in which the Fe-termination is high relative to the O-termination, and the reverse. The different domain borders have significantly different heights, consistent with RTM calculations. This agreement allows us to conclude that the Fe-termination is topographically high on most terraces. Surface domains are observed in aqueous solutions at the atomic scale, and appear to be very unreactive on tens-of-seconds time scales at pH 1.