Computer simulation of the structure and stability of forsterite surfaces

The aim of this paper is to demonstrate that atomistic simulations can be used to evaluate the structure of mineral surfaces and to provide reliable data for forsterite surfaces up to a plane index of 2 using the code METADISE. The methods used to calculate the surface structure and energy which have more commonly been used to study ceramics are briefly explained as is a comparison with experimental data, most notable the crystal morphology. The predicted morphologies show that all the methods (Donnay-Harker, Attachment energies and equilibrium) show most of the surfaces that are expressed in observed crystals. The equilibrium morphology calculated from the relaxed surface energies is the only method which expresses the {201} surfaces and the {101} surfaces, which appear only upon relaxation. The more stable surfaces are shown to be those which have the highest surface density and more closely resemble close packed structures with highly coordinated surface ions and silicon as far from the surface as possible. The most stable surfaces the {100} which has alternating layers of MgO and SiO₂ terminating with an MgO layer. The structure is similar to the MgO {100} surfaces and has a similar energy (1.28?Jm^?2 compared to 1.20). The second most stable are the {201} which have a stepped surface topology, but is also compact with a relaxed surface energy of 1.56?Jm^?2. The results indicate that atomistic simulation is well suited to the prediction of surface structure and morphology although care must be taken in choosing potentials which model the structure and elastic properties accurately.     

Effect of trends on correlation in open and closed three-component systems

It is well known among geologists that closure of an open-number system, as when stratigraphic rock thicknesses are converted to percentages, introduces correlations among the components even in the absence of correlations in the open system. In closed three-component systems the covariances are single-valued functions of the closed variances and are exactly predictable. If the open system has inherent correlation (point correlations) among its components the corresponding closed covariances reflect their presence in a predictable manner. If areal trends are present in the open system, the open covariances are themselves affected, but this trend effect can be completely removed to recover the initial point correlations among the components. Areal trends in open systems strongly influence the structure of the closed variance-covariance matrices, and the situation becomes increasingly complicated if the open system has both point correlations and areal trends. The paper considers the problems involved, and includes Monte Carlo runs to compare computed and predicted variances and covariances as data sets are followed from open systems with correlation but no trend to the closed equivalent of open systems with point correlations and trends.     

Remote leveling of tide gauges using GNSS reflectometry: case study at Spring Bay,Australia

We further developed a new approach using GNSS reflectometry to determine the leveling connection between a tide gauge and a GNSS antenna. This approach includes the optimization of the unknown receiver bandwidth and the estimation of frequency changes in the signal-to-noise ratio (SNR) oscillation through an extended Kalman filter/smoother algorithm. We also corrected the geometric bending of the GNSS signals due to tropospheric refraction using local meteorological observations. Using 3 weeks of SNR data in Spring Bay, Australia, from a GNSS antenna placed sideways (i.e., ground plane orientated vertically and directed in azimuth toward the sea surface) to improve the SNR interference near the horizon, we obtained mean leveling differences of approximately 5 mm, with an RMS of approximately 3 cm level with respect to the nominal leveling from classical surveying techniques. SNR data from three different receiver manufacturers, coupled to the same antenna, provided similar leveling results. With a second antenna in the usual upright configuration, we obtained mean leveling differences of 1–2 cm and a RMS of about 10 cm. In the upright configuration, the leveling differences may include errors in the GNSS antenna phase center calibration, which are avoided in our technique but not in the classical surveying techniques. These results demonstrate the usefulness of the reflectometry technique to obtain precisely and remotely the leveling between a GNSS antenna and a tide gauge. In addition, this technique can be applied continuously, providing an independent and economical means to monitor the stability of the tide gauge zero.     

STATISTICAL METHODS IN ROCK MAGNETISM

Summary. This paper describes the statistical techniques available to the experimenter in palaeomagnetic work. The theory of these methods is based on an assumed probability distribution of errors. It is shown that the mathematical requirements of this distribution are obeyed by the observations from rock samples which are known to possess a stable magnetization; observations on rocks with unstable magnetization however do not conform to it. A theoretical derivation is given for this probability distribution.
The problem of estimating the mean direction of magnetization of a geological formation has in recent years become a matter of the greatest geophysical interest since it is from such estimates that the position of the pole of the Earth in past geological ages is determined. This problem is largely one of the judicious choice of samples and a procedure is suggested whereby such estimates may be achieved with the greatest sample economy.     

Calibrations to estimate absolute numbers of New Zealand fur seal (Arctocephalus forsteri) pups from direct counts

Annual direct counts of seal pups can indicate long‐term trends in population size, but mark‐recapture estimates are needed to deduce absolute numbers. A calibration between results from these two methods would facilitate the use of direct counts to estimate absolute numbers, an outcome that is relatively quick, cheap and minimises disturbance of animals. Mark‐recapture estimates for the numbers of New Zealand fur seal (Arctocephalus forsteri) pups in 2003 at 10 colonies at Otago, southeastern New Zealand, were compared with independent single counts at the same colonies. A single ratio to estimate absolute numbers (y) from direct counts x was not statistically significant. Instead, two ratios were deduced, based on differences in habitat among colonies: y = 1.51x for colonies with hiding places for pups and y = 0.96x for colonies without hiding places. Application of these calibrations and their 95% prediction intervals produce estimates and ranges for the absolute numbers of pups from single annual counts.     

Oxygen self-diffusion “fast-paths” in titanite single crystals and a general method for deconvolving self-diffusion profiles with “tails”

Like most other minerals, titanite rarely if ever forms perfect crystals. In addition to the point defects that might affect lattice diffusion, there may be extended line- or planar defects along which fast diffusion could occur. During the course of an experimental study of oxygen lattice diffusion in titanite, we found that almost all of the ¹⁸O uptake profiles produced in natural titanite crystals departed from the complementary error function solution expected for simple lattice diffusion with a constant surface concentration. Instead, they exhibited “tails” extending deeper into the samples than expected for simple lattice diffusion. The purpose of this contribution is to report on these features—described as “fast-paths” for oxygen diffusion—and outline a method for coping with them in extracting information from diffusion profiles.For both dry and hydrothermal experiments in which the “fast paths” are observed, ¹⁸O was used as the diffusant. In dry experiments, the source material was ¹⁸O-enriched SiO₂ powder, while ¹⁸O-enriched water was used for the hydrothermal experiments. Diffusive uptake profiles of ¹⁸O were measured in all cases by nuclear reaction analysis (NRA) using the ¹⁸O (p,α)¹⁵N reaction [see Zhang X. Y., Cherniak D. J., and Watson E. B. (2006) Oxygen diffusion in titanite: lattice and fast-path diffusion in single crystals. Chem. Geol.235 105-123].In our experiments, different sizes of “tails” (with varying ¹⁸O concentrations) were observed. Theoretically, under the same temperature and pressure conditions, the sizes of tails should be affected by two factors: the diffusion duration and the defect density. For the same experiment duration, the higher the defect density, the larger the “tail”; for the same defect densities, the longer the diffusion duration, the larger the “tail.”The diffusion “tails” could be a result of either planar defects or one-dimensional “pipe” diffusion. AFM imaging of HF etched titanite surfaces confirmed that the etched features might be caused by either parallel planar defects or parallel pipe defects, but could not differentiate between these possibilities. Through theoretical calculations simulating the tailed diffusion profiles using reasonable assumptions of lattice diffusivities and fast-path diffusivities, and comparing these with tail features measured in our samples, it can be concluded that the “tails” observed in our experiments are caused by planar defects rather than pipe defects.A new method was developed for separating the “fast-path” contribution from the overall composite diffusion profile consisting of both “fast-path” and lattice diffusion. Through this process, the lattice diffusion coefficient could be determined, which is required to analyze the tail. The oxygen diffusion rates in the fast-paths were obtained by traditional graphical analysis methods, using the Whipple-Le Claire equation (for 2-D defects) assuming that the width of the fast-path is 1 nm. Two Arrhenius relations were obtained for the fast-path diffusion phenomenon, one for experiments under dry conditions, and the other for hydrothermal conditions:

     

Late holocene environmental change in an upper Montane area of the snowy mountains,New South Wales

This study examines environmental change in the upper montane zone of the Australian Eastern Highlands during the late Holocene, by analysing vegetation, fire and erosion records contained within a small fen located in a frost hollow. Differences in environmental parameters across the prehistoric—historic boundary were particularly investigated in an attempt to characterise better the changes associated with the imposition of European land‐use practices. Decreases in arboreal pollen and an increased charcoal concentration near the base of the analysed sequence, interpreted to be about 1600 y BP until about 1300 y BP, are suggestive of reduced moisture availability. After this, a period of relative stability continued to the close of the prehistoric period. The arrival of Europeans in the region triggered changes in the sediment record, including an increase in the accumulation of sediment by an order of magnitude, and changes in the surrounding vegetation. Saturated isothermal remnant magnetism (SIRM) was found to be significantly higher in the historic period compared to the analysed prehistoric period, suggesting an alteration in the erosional processes within the catchment. The concentration of charcoal was comparable between the prehistoric and historic periods; however, the increased sedimentation rate of the historic period infers an increased accumulation of charcoal. Fire did not appear to be related to the vegetation changes evident in the historic period, perhaps due to the use of cool fires by the pastoralists.     

Spatial and seasonal variations in the chemistry of sediment interstitial waters in the Tamar Estuary

Chemical concentration gradients in the interstitial waters of shallow (0–10 cm), reducing sediments are reported for four stations in the Tamar Estuary over a two-year period. The products of organic matter breakdown, sedimentary redox changes and diagenetic reactions have been determined and a multicomponent analytical approach has enabled the interactions of complementary processes to be examined. While many components show spatial and seasonal patterns related to the supply of organic matter and salinity associated sulphate distribution, the effects of temperature, sediment disturbance and river flow are also apparent.Sediment stored prior to the separation of interstitial water showed significant changes in chemical composition compared to samples processed within 24 h of collection.