Kinetic studies of the rate of dissolution of silica and diatom tests in sea water

Kinetic studies have been carried out on the dissolution of 10μm beads of silica and of the siliceous tests of two species of diatoms (Thalassiosira fluviatus andSkeletonema costatum) in sea water at 10–50°C and over the pH range 6–9. At all temperatures dissolution of the biogenous silica occurred most rapidly at pH 8 and most slowly at pH 6. First order kinetics were closely followed when the silica was present in a considerable excess over that required for saturation, the rate being proportional to the area of the silica. Apparent deviation from this type of kinetics occurred when there was insufficient silica to bring about saturation. This was undoubtedly due to the progressive decrease in the surface area which takes place as the particle dissolves. Application of the rather simplistic model developed by Kamataniet al. (1980), which makes allowance for this decrease, gave a close correspondence with the data until ∼ 90% of the silica had dissolved.     

Crystallization processes in an artificial magma: variations in crystal shape,growth rate and composition with melt cooling history

A large (4.8 m³, 1.3x10⁷ g) artificial mafic melt with a bulk composition similar to that of a basalt (but with a high CaO content of 17 wt%) was generated during a demonstration of in situ vitrification and was allowed to cool naturally. During the melting process, convection was vigorous, resulting in a chemically and thermally homogeneous melt body. Once heating was complete, the cooling rate was rapid with the temperature dropping from 1500°C to 500°C in 6 days within the interior of the 3 m diameter, 1.5 m thick body. A 20 h period of constant temperature (1140°C) observed during colling was the result of latent heat released by widespread crystallization. The final crystalline assemblage consists of diopsidic to hedenbergitic pyroxene and anorthitic feldspar, with a subordinate amount of potassic feldspar, plus a small amount of evolved glass. The compositions and proportions of phases agree well with those predicted by the MELTS thermodynamic model. Thermal and textural evidence suggest that convection within the melt ceased coincident with formation of the first crystals. Textural investigation of core samples reveals large (up to 1 cm in length) acicular diopsidic pyroxenes in a matrix of smaller feldspar and zoned pyroxene crystals (500 m in length). Crystal shape and pyroxene composition vary as a function of position within the solidified body, as a function of cooling rate. Both crystal size and degree of crystallinity are highest in the central, most slowly-cooled parts of the rock. Crystal shape is characterized by tabular, equilibrium-growth forms in the slowly-cooled areas, grading to highly skeletal, dendritic forms at the rapidly-cooled edges of the body. The pyroxene crystals are dominantly homogeneous diopside, but crystals are characterized by thin Fe-rich hedenbergitic rims. These rims were deposited when Mg in the melt was depleted by diopside growth, and melt temperature had cooled sufficiently to allow Fe-rich pyroxene growth. Crystal growth rates can be calculated based on thermal behavior of the melt, reinforced by thermodynamic modelling, and are determined to be between 10^-7 and 10^-8 cm/s in the central part of the melt. These estimates agree well with growth rates in natural systems with similar cooling rates. Pyroxene crystals that formed at a higher cooling rates are characterized by higher Al and lower Mg contents relative to tabular equilibrium crystalline forms, presumably as a result of disequilibrium melt compositions at the crystal-melt interface.New Mexico Bureau of Mines and Mineral Resources, New Mexico Institute of Mining and Technology, Socorro, NM 87801, USA     

Distribution and morphology of sinkholes triggered by flooding following Tropical Storm Alberto at Albany, Georgia, USA

Flooding of the Flint River in July 1994 triggered the collapse of at least 312 sinkholes in the karstic Dougherty Plain at Albany, Georgia. We examined the distribution and morphology of these new sinkholes to evaluate the mode of formation, to characterize early stages of the evolution of sinkhole form, and to estimate the lowering of the surface associated with the development of new sinkholes.Eighty-eight percent of sinkholes occur inside the limits of flooding, especially in areas of sandy overburden, and they often follow joint-controlled linear trends. Sinkhole dimensions are log-normally distributed with median values of circumference = 5.7 m, length = 1.8 m, width = 1.6 m, and depth = 0.7 m; asymmetry (L:W) = 1.2. Cross-sectional forms range from narrow cylinders to large bowls, with many sinkholes having undercut sides.Flooding triggered the formation of sinkholes by saturating and liquefying overburden, which caused soil arches to collapse and flow into cavities in bedrock. The prevalence of sinkholes near the periphery of flooding suggests that drainage and loss of buoyant support as flood waters subsided may also have contributed to failure. A volume ratio index is used to quantify the three dimensional geometric form of sinkholes. Initially, small cylindrical shafts open over a bedrock joint, followed by progressive slumping that leads to widening and increases in volume to a final bowl form. Estimates of the aggregate volume of overburden transported underground in flooded areas range from 7,990 to 11,130 m3. Averaged over flooded areas, this accounts for 0.26 to 0.37 mm/km² lowering of the surface. Based on a 500 year recurrence interval for the flood event, values for lowering of the surface range from 0.52 to 0.74 mm per 1,000 years. These values are an order of magnitude less than estimates of carbonate dissolution and suggest that transport of overburden underground is limited by triggering events.     

Quantum-thermodynamic treatment of intrinsic anharmonicity; Wallace’s theorem revisited

Wallace (in Thermodynamics of crystals, 1972) developed a theorem, rooted in rigid lattice dynamics, which incorporates intrinsic anharmonic effects in solids. The practical application of this theorem in mineral physics is computationally involved and this is the main reason for the theorem not getting the attention it deserves. Because intrinsic anharmonicity is an important issue at the extreme conditions in planetary mantles, we derived a method which removes the computational obstacles in applying this theorem. We extended the theorem to incorporate details of the phonon spectrum and tested our algorithm on forsterite (Mg₂SiO₄). Using a least squares inversion technique applied to all available experimental data, we show that it results in an accurate representation of thermodynamic properties and sound wave velocities of Mg₂SiO₄ in its complete pressure–temperature stability range. We also show that the accuracy of our results is not significantly affected by the use of a different equation of state.     

Analysis of the surface temperature and wind forecast errors of the NCAR-AirDat operational CONUS 4-km WRF forecasting system

Investigating the characteristics of model-forecast errors using various statistical and object-oriented methods is necessary for providing useful guidance to end-users and model developers as well. To this end, the random and systematic errors (i.e., biases) of the 2-m temperature and 10-m wind predictions of the NCAR-AirDat weather research and forecasting (WRF)-based real-time four-dimensional data assimilation (RTFDDA) and forecasting system are analyzed. This system has been running operationally over a contiguous United States (CONUS) domain at a 4-km grid spacing with four forecast cycles daily from June 2009 to September 2010. In the result an exceptionally useful forecast dataset was generated and used for studying the error properties of the model forecasts, in terms of both a longer time period and a broader coverage of geographic regions than previously studied. Spatiotemporal characteristics of the errors are investigated based on the 24-h forecasts between June 2009 and April 2010, and the 72-h forecasts between May and September 2010. It was found that the biases of both wind and temperature forecasts vary greatly seasonally and diurnally, with dependency on the forecast length, station elevation, geographical location, and meteorological conditions. The temperature showed systematic cold biases during the daytime at all station elevations and warm biases during the nighttime above 1,000 m above sea level (ASL), while below 600 m ASL cold biases occurred during the nighttime. The forecasts of surface wind speed exhibited strong positive biases during the nighttime, while the negative biases were observed in the spring and summer afternoons. The surface wind speed was mostly over-predicted except for the stations located between 1,000 and 2,100 m ASL, for which negative biases were identified for most forecast cycles. The highest wind-speed errors were found over the high terrain and near sea-level stations. The wind-direction errors were relatively large at the high-terrain elevation in the Rocky and Appalachian mountain ranges and the western coastal areas and the error structure exhibited notable diurnal variability.     

Lightning fatalities in Australia, 1824–1991

Information on fatalities from lightning strikes has been extracted from a specially compiled database on natural hazards in Australia. Records dating from 1803–1991 indicate that at least 650 persons have been killed by lightning strikes. Maps and charts show the percentages of victims with respect to age, sex, locality, activity, and other circumstances of the strike. The majority of the 650 fatalities recorded have occurred along the more populous southeastern coast. The overall death rate, from 1910–1989, is 0.08 per 100 000 population. The annual number of lightning fatalities has decreased with time, from a death rate of 0.21 in 1910–1919 to 0.01 in 1980–1989. This trend is more pronounced when population figures are taken into account. The group that has been most at risk in Australia is that of males aged 15–19, followed by males aged 20–34. The male:female ratio of victims has decreased with time but is not approaching equality, being 11.6 in 1910–1919 and 5.3 in 1980–1989. The diurnal and monthly occurrences of lightning fatalities peak at 12.00–18.00 hours and November-February respectively. About 86% of fatalities have occurred outdoors and 14% have occurred indoors. Approximately three-fifths of fatalities have been work-related, and the group of workers that has traditionally been most at risk is that of land-workers. Approximately one-fifth of fatalities have been recreation-related, although this proportion has been increasing with time. The recreational activities of water sports, golf, and cricket have had the greatest number of lightning fatalities. Comparisons are made between these data and the results of other similar studies, both in Australia and overseas.     

The normal-force coefficient of a thin closed fence

In a full-scale field study, the drag coefficient of a thin closed fence was estimated. A measurement plate was constructed more or less in the center of the barrier in order to estimate the normal-force on the fence. The normal-force coefficient was studied under near-neutral stratification for various Reynolds numbers and different angles of attack.     

Environmental oxidation rate of manganese(II): bacterial catalysis

A simple mass balance for dissolved manganese(II) in waters containing low levels of oxygen in Saanich Inlet indicates that the residence time for Mn(II) removal to the solid phase is on the order of a few days. The average oxidation state of Mn in particulate material sampled from the region of Mn removal was 2.3–2.7, and electron micrographs revealed structures characteristic of bacterially formed Mn precipitates. Radiotracer experiments utilizing ⁵⁴Mn(II) indicated that removal of Mn from solution in the region of active uptake was substantially blocked by a poison mixture, demonstrating that Mn(II) binding to particulates is catalyzed by bacteria in this environment.