Characterisation of brown coal humic acids and modified humic acids using pyrolysis gcms and other techniques

It has been proposed that Victorian brown coal can be considered as a two-component structure — a lignocellulosic “host”, containing various amounts of weakly bound or entrapped “guest” material together with very small amounts of inorganic and/or mineral matter. The latter predominantly consists of wax esters and/or terpenoid material. In this paper we describe attempts to gain structural information regarding the more complex, “host” component of the coal. Our initial model compound has been humic acid that can be readily obtained from the coal by alkaline extraction. It has been found that “pure” humic acid, free from material associated with the “guest” components of the coal, can be obtained by a highly selective, low-yielding alkaline extraction. This humic acid has been studied by nmr spectroscopy and pyrolysis gas chromatography-mass spectroscopy (py-gc/ms). The products arising from py-gc/ms have been compared with those obtained from similar pyrolysis of whole coals. Alkylation of humic acids using alkyl halides in the presence of base has been successfully carried out and reactivity of the resulting materials compared with those of the parent coal and humic acid.     

Frequency dependence of elastic wave speeds at high temperature: a direct experimental demonstration

At sufficiently high temperatures and/or long periods, the elastic behaviour of crystalline material gives way progressively to viscoelastic behaviour associated with the stress-induced migration of crystal defects. This transition is marked by the onset of appreciable strain energy dissipation accompanied by frequency dependence (dispersion) of the shear modulus and elastic wave speeds. Ultrasonic interferometry and torsional forced-oscillation techniques can be used to probe the low-amplitude stress-strain behaviour of fine-grained polycrystalline material in two very different frequency ranges, respectively 10-100 MHz and 1 mHz-1 Hz. Here we demonstrate and apply these two complementary methods in a study of the high-temperature mechanical behaviour of a fine-grained synthetic olivine polycrystal. At the high frequencies of ultrasonic interferometry, the shear wave speed varies linearly with temperature between room temperature and the highest experimentally accessible temperature (1300 °C) in close accord with expectations based on similarly high-frequency studies of the elastic behaviour of single-crystal olivine. However, at teleseismic frequencies (<1 Hz) and temperatures >900 °C, the shear wave speed becomes much more strongly temperature-sensitive reflecting markedly viscoelastic behaviour. Newly emerging laboratory-derived constraints on this viscoelastic enhancement of the temperature sensitivity of seismic wave speeds and its grain-size dependence will provide a more robust interpretation of seismological models for the variation of wave speeds and attenuation within the Earth's interior.     

Rock albedo and monitoring of thermal conditions in respect of weathering: some expected and some unexpected results

Broadly speaking, there is, at least within geomorphic circles, a general acceptance that rocks with low albedos will warm both faster and to higher temperatures than rocks with high albedos, reflectivity influencing radiative warming. Upon this foundation are built notions of weathering in respect of the resulting thermal differences, both at the grain scale and at the scale of rock masses. Here, a series of paving bricks painted in 20 per cent reflectivity intervals from black through to white were used to monitor albedo‐influenced temperatures at a site in northern Canada in an attempt to test this premise. Temperatures were collected, for five months, for the rock surface and the base of the rock, the blocks being set within a mass of local sediment. Resulting thermal data did indeed show that the dark bricks were warmer than the white but only when their temperatures were equal to or cooler than the air temperature. As brick temperature exceeded that of the air, so the dark and light bricks moved to parity; indeed, the white bricks frequently became warmer than the dark. It is argued that this ‘negating’ of the albedo influence on heating is a result of the necessity of the bricks, both white and black, to convect heat away to the surrounding cooler air; the darker brick, being hotter, initially convects faster than the white as a product of the temperature difference between the two media. Thus, where the bricks become significantly hotter than the air, they lose energy to that air and so their respective temperatures become closer, the albedo influence being superceded by the requirement to equilibrate with the surrounding air. It is argued that this finding will have importance to our understanding of weathering in general and to our perceptions of weathering differences between different lithologies. Copyright © 2005 John Wiley & Sons, Ltd.     

A resistivity section of Holy Island (Anglesey)

An account is given of the use of square array resistivity techniques to derive an apparent resistivity section down the length of Holy Island (Anglesey). Possible interpretations of this section in terms of the distribution of true resistivity with depth are given and discussed briefly in relation to proposed geological structure.     

Andesite and dacite genesis via contrasting processes: the geology and geochemistry of El Valle Volcano,Panama

The easternmost stratovolcano along the Central American arc is El Valle volcano, Panama. Several andesitic and dacitic lava flows, which range in age 5–10 Ma, are termed the old group. After a long period of quiescence (approximately 3.4 Ma), volcanic activity resumed approximately 1.55 Ma with the emplacement of dacitic domes and the deposition of dacitic pyroclastic flows 0.9–0.2 Ma. These are referred to as the young group. All of the samples analyzed are calc-alkaline andesites and dacites. The mineralogy of the two groups is distinct; two pyroxenes occur in the old-group rocks but are commonly absent in the young group. In contrast, amphibole has been found only in the young-group samples. Several disequilibrium features have been observed in the minerals (e.g., oscillatory zoning within clinopyroxenes). These disequilibrium textures appear to be more prevalent among the old- as compared with the young-group samples and are most likely the result of magma-mixing, assimilation, and/or polybaric crystallization. Mass-balance fractionation models for major and trace elements were successful in relating samples from the old group but failed to show a relationship among the young-group rocks or between the old- and young-group volcanics. We believe that the old-group volcanics were derived through differentiation processes from basaltic magmas generated within the mantlewedge. The young group, however, does not appear to be related to more primitive magmas by differentiation. The young-group samples cannot be related by fractionation including realistic amounts of amphibole. Distinctive geochemical features of the young group, including La/Yb ratios〉15, Yb〈1, Sr/Y〉150, and Y〈6, suggest that these rocks were derived from the partial melting of the subducted lithosphere. These characteristics can be explained by the partial melting of a source with residual garnet and amphibole. Dacitic material with the geochemical characteristics of subducted-lithosphere melting is generated apparently only where relatively hot crust is subducted, based on recent work. The young dacite-genesis at El Valle volcano is related to the subduction of relatively hot lithosphere.     

Zircon textures and composition: refractory recorders of magmatic volatile evolution?

Zircon textures and composition have been used to infer magmatic processes including closed-system fractional crystallization, magma mixing or replenishment, and country-rock assimilation. Here, we propose that zircon textures and composition may also be refractory recorders of magmatic volatile evolution. We present field, whole-rock chemical, textural, mineral chemical, and U–Pb age data from evolved, fine-to-coarse-grained granite intrusions on Melville Peninsula, Nunavut, Canada. Zircon forms two main populations in these granites, Type-1 and Type-2 zircon. Type-1 zircon is present in all samples, but predominant in fine-grained granite. Crystals are euhedral and inclusion-rich and show periodic, fine-scale oscillatory zoning, comparatively low concentrations of U (<2,200 ppm) and Hf (<1.6 wt%), high Zr/Hf (~40–62), and pervasive alteration. Type-2 zircon is predominant in coarse-grained granite. Crystals form overgrowths on Type-1 zircon and individual crystals. They are subhedral and inclusion-poor and show weak, irregular, large-scale oscillatory zoning, high U (up to ~7,250 ppm) and Hf (1.5–2.0 wt%), low Zr/Hf (~37–44), and only local alteration. Compatible trace-element concentrations and Zr/Hf change sharply across the boundary of Type-1 to Type-2 zircon; ²⁰⁷Pb/²⁰⁶Pb ages preclude a significant hiatus between crystallization of the two types. We argue against magmatic versus hydrothermal crystallization, country-rock assimilation, or magma mixing as causes for the crystallization of Type-1 and Type-2 zircon. We propose instead that Type-1 zircon formed from volatile-undersaturated magmas and that Type-2 zircon formed from volatile-saturated magmas. Magmas fractionated by volatile-driven filter pressing into crystal-rich mush and crystal-poor magma. Crystal-rich mush with abundant Type-1 zircon crystallized to fine-grained granite. Volatile-rich magma crystallized to Type-2 zircon and coarse-grained granite. While Type-1 zircon was pervasively altered by exsolving magmatic volatiles, Type-2 zircon was only locally affected by subsolidus hydrothermal alteration.     

Gum rosin (colophony): A suitable material for thermomechanical modelling of the lithosphere

We investigate the use of a ductile material with temperature-sensitive viscosity for thermomechanical modelling of the lithosphere. First, we consider the scaling of mechanical and thermal properties. For a normal field of gravity, the balance of stresses and body forces sets the stress scale, in proportion to the linear dimensions and the densities. The equation of thermal conduction sets the time scale. The activation enthalpy for creep sets the temperature scale; but the thermal expansivity provides an additional constraint on this temperature scale.

Gum rosin appears to be a suitable material for lithospheric modelling. We have measured its flow properties, at various temperatures, in a specially designed rotary viscometer with unusually low machine friction. The rosin is almost Newtonian. Strain rate depends upon stress to the power n, where 1.0 <n < 1.14. The viscosity varies over 5 orders of magnitude, from about 10² Pa s at 80°C, to about 10⁷ Pa s at 40°C. The activation enthalphy is thus about 250 kJ/mol. Measured with a needle probe, the thermal conductivity is 0.113 ± 0.001 W m⁻¹K⁻¹; the thermal diffusivity, (6±3) ×10⁻⁷ m² s⁻¹. Calculated from X-ray profiles, the thermal expansivity is about 3 × 10⁻⁴ K⁻¹. These thermal and mechanical properties make gum rosin suitable for thermomechanical models, where linear dimensions scale down by a factor of 10⁶; time, by 10¹¹; viscosity, by 10¹⁷; and temperature change, by 10¹.