Settlement and sustainability in the Polish Sudetes

The paper summarises the history of human settlement in the Sudetes from the Bronze Age. A more intensive stage was reached in the Middle Ages when settlers from the west established new villages deep in the mountain valleys. By the beginning of the 20th century the Sudetes were already overpopulated but after a near-complete ethnic replacement from a German to a Polish population in 1945–8, population continued to grow until the 1980s. However, the economic system was hardly sustainable by this time. There were many polluting industries in the region and massive transboundary pollution from adjacent areas of Czechoslovakia and Germany had a devastating effect on the forests. Moreover, subsidised state agriculture placed heavy pressure on vulnerable mountain grazings. Since 1989 there has been a process of deindustrialisation in the Sudetes and surrounding areas and, with the disappearance of the state farms and the reduction in subsidies, agriculture is now better adjusted to the natural potential and is complemented by a promising start with agrotourism. The population of the region is growing relatively slowly (0.8% per annum 1956–1999), with the rural areas now in decline. A sustainable future for the region is now a possibility, but while there is a consensus for continued environmental reconstruction, supported by alternative economies, this will have to be carefully managed in the years ahead when EU accession may bring heavier development pressures than those evident at the moment. This revised version was published online in July 2006 with corrections to the Cover Date.     

The geochemistry of primary and weathered oil shale and coquina across the Julia Creek vanadium deposit (Queensland, Australia)

A significant resource of vanadium and molybdenum exists near Julia Creek, Australia, where the middle Cretaceous organic-rich Toolebuc Formation lies between 0 and 25 m of the surface. We present and discuss a comprehensive geochemical study of the Toolebuc Formation and its enclosing stratigraphy near Julia Creek to understand this ore deposit. V and Mo contents in fresh facies are strongly associated with total organic carbon (TOC) contents, but not with Al or CaCO₃; this suggests that V and Mo were originally concentrated in the organic fraction. However, chemical extractions using H₂O₂ indicate that Mo was originally concentrated in pyrite. The data also suggest that V was mobilised from organic matter during early diagenesis and became associated with clays as little V was extracted by H₂O₂ in the fresh samples. TOC contents in the Toolebuc Formation were removed during weathering, residually enriching trace metals including V and Mo, and as a result, the TOC relationship with V and Mo disintegrates. With weathering, both V and Mo predominantly became associated with iron oxide/hydroxide phases (and possibly other unidentified phases) as these elements in the weathered facies were highly soluble in the sodium citrate–sodium dithionite digestion. Large shale-hosted V and Mo deposits such as Julia Creek offer a potentially viable alternative to the currently mined magnetite-hosted deposits. A thorough understanding of the formation and host mineral phases for V and Mo of these shale deposits, however, is critical to ensure that these valuable metals can be feasibly extracted.     

Structure proof and significance of stereoisomeric 28,30-bisnorhopanes in petroleum and petroleum source rocks

Two C₂₈H₄₈-pentacyclic triterpanes were isolated from Monterey shale. X-ray crystallography of a crystal containing both compounds proved their structures as 17β,18α,21α(H)-28,30-bisnorhopane and 17β,18α,21β(H)-28,30-bisnorhopane. Several differences are found between 28,30-bisnorhopanes and the regular hopanes. Unlike the regular hopane epimers, for practical purposes the three epimeric 28,30-bisnorhopanes [17α,21β(H)-, 17β,21α(H)-, and 17β,21β(H)-]cannot be distinguished by their mass spectra. Special conditions are needed to separate them by gas chromatography. The diagenetically first-formed epimer is thought to be 17α,21β(H)- because it predominates in immature shales. The order of thermodynamic stability is 17β,2lα(H) < > 17α,21β(H) > 17β,21β(H), and all three epimers are present in petroleum. 25,28,30-Trisnorhopanes can be analyzed in similar fashion and are found to have similar thermodynamic characteristics. The percent of the ring D/E cis epimer of 28,30-bisnorhopane and/or 25,28,30-trisnorhopane is a useful maturation parameter similar to the 20S/20R sterane ratio. Evidence indicates 25-demethylation of 28,30-bisnorhopane to 25,28,30-trisnorhopane during advanced stages of biodegradation. Hence, percent ring $\text{D}\text{E}$cis 25,28,30-trisnorhopane has an application to maturation assessment in heavily biodegraded oils.     

Recent progress on combining geomorphological and geochronological data with ice sheet modelling,demonstrated using the last British–Irish Ice Sheet

Palaeo-ice sheets are important analogues for understanding contemporary ice sheets, offering a record of ice sheet behaviour that spans millennia. There are two main approaches to reconstructing palaeo-ice sheets. Empirical reconstructions use the available glacial geological and chronological evidence to estimate ice sheet extent and dynamics but lack direct consideration of ice physics. In contrast, numerically modelled simulations implement ice physics, but often lack direct quantitative comparison with empirical evidence. Despite being long identified as a fruitful scientific endeavour, few ice sheet reconstructions attempt to reconcile the empirical and model-based approaches. To achieve this goal, model-data comparison procedures are required. Here, we compare three numerically modelled simulations of the former British–Irish Ice Sheet with the following lines of evidence: (a) position and shape of former margin positions, recorded by moraines; (b) former ice-flow direction and flow-switching, recorded by flowsets of subglacial bedforms; and (c) the timing of ice-free conditions, recorded by geochronological data. These model–data comparisons provide a useful framework for quantifying the degree of fit between numerical model simulations and empirical constraints. Such tools are vital for reconciling numerical modelling and empirical evidence, the combination of which will lead to more robust palaeo-ice sheet reconstructions with greater explicative and ultimately predictive power.     

A kinetic model of metamorphism: an application to siliceous dolomites

We use a kinetic model of a metamorphic system to study the effect of competing rates of reaction, fluid injection, and heating on the evolution of the reaction pathway in temperature/composition space at constant pressure. We show that for rocks in contact with mixed volatile (e.g., CO₂-H₂O) fluids the reaction path may be quite different from what is expected from equilibrium-based petrologic models. Equilibrium-based models, used to understand the development of rock systems undergoing mineral reactions during a metamorphic event, rely on the Gibbs phase rule and only consider stable phases. For constant pressure, the temperature-composition paths follow univariant curves and significant reactions may occur at invariant points. By contrast, the more general kinetic treatment is not constrained by equilibrium, although with the proper competing rates equilibrium is a possible endmember of the kinetic approach. The deviation from equilibrium depends on the competing rates of reaction, heating, and fluid injection. A key element required by the kinetic approach is the inclusion of metastable reactions in the formulation, whereas such reactions are irrelevant for equilibrium-based models. Metastable reactions are often involved in a complex interplay with common prograde stable metamorphic reactions. We present model results for the well-studied CaO-MgO-SiO₂-CO₂-H₂O (CMS) system to show how the system evolves under kinetic control. Our simulations and discussion focus on the behavior of the CMS system under a number of closed and open system conditions. Special attention is paid to closed system behavior in the vicinity of the (first) isobaric invariant point (with Dol, Qtz, Tlc, Cal, and Tr). Also, for open systems with massive fluid infiltration we consider heating rates varying from contact to regional metamorphic conditions. For some geologically reasonable rates of reactions, heating, and fluid injection, our results demonstrate that equilibrium conditions may be significantly overstepped in metamorphic systems. We used overall mineral reactions in this model with rates based on experimental results. Future models could rely on more fundamental dissolution and precipitation reactions. Such an extension would require additional kinetic rate data, as well as mineral solubilities in mixed volatile fluids.Editorial responsibility: J. Hoefs     

Orthophosphate and biotite chemistry from orthopyroxene-bearing migmatites from California and South India: The role of a fluid-phase in the evolution of granulite-facies migmatites

Migmatites from Cone Peak, California, USA and the Satnur-Sangam road, Southern Karnataka, India contain coarser grained orthopyroxene-bearing leucosomes with subordinate biotite in finer grained hornblende-biotite-pyroxene-bearing hosts. At both localities the leucosomes are enriched in quartz and feldspar and have a higher ratio of pyroxene to hornblende + biotite compared to the host rocks. Biotite grains in leucosomes along the Satnur-Sangam road are concentrated at the margins of orthopyroxene grains and have lower abundances of Ti, Fe, and Cl and a higher abundance of F than biotite grains from the host rock. Fluorapatite grains in all rocks from both localities contain monazite inclusions similar to those produced experimentally by metasomatically induced dissolution and reprecipitation. Some fluorapatite grains at both localities are partially rimmed by allanite. The only compositional differences found between fluorapatite grains in the leucosomes and host rocks were higher concentrations of Cl in grains in leucosomes from Cone Peak. The mineralogies of the rocks suggest that the leucosomes formed by dehydration melting reactions that consumed feldspar, quartz, hornblende, and biotite and produced orthopyroxene. Allanite rims at the margins of fluorapatite grains may have formed by the later retrogression of monazite rims formed by incongruent dissolution of fluorapatite in the melt. Biotite grains at the margins of orthopyroxene crystals in the leucosomes from the Satnur-Sangam road apparently formed by retrogression of orthopyroxene upon the solidification of the anatectic melt. A similar high-grade retrogression did not affect orthopyroxene crystals at Cone Peak, indicating that H₂O was removed from the crystallizing leucosomes probably in a low H₂O activity fluid. Compositional differences between the paleosome and neosomes at Cone Peak are best explained by metasomatic interaction with concentrated brines while elevated Cl concentrations in fluorapatites in the leucosome suggest interaction with a Cl-bearing fluid. Brines may have been responsible for an exchange of elements between the host rock along the Satnur-Sangam road and zones of melt generation now marked by leucosomes, but fluid flow appears to have been less vigorous than at Cone Peak.     

On the kinetics of volatile loss from chondrites

We have re-examined data by Lipschutz and coworkers on thermal release of T1, Bi, In from primitive chondrites, in order to obtain information on the nature and activation energy (E) of the release processes: desorption, volume diffusion, and decomposition of the host phase. Plausible though not definitive choices may be made in some cases. For the Allende C3 chondrite, the main release for Bi and T1 (80 and 86%) between 400 and 700°C appears to be due to desorption of a surface layer, coupled with grain boundary diffusion as the slow step. The main release of In (80%) above 600°C and the small (10–20%) tails of Bi and T1 between 700 and 1000°C probably represent volume diffusion, with activation energies near 30 kcal/mol. The much smaller E's (2–5 kcal/mol) found for this interval by the Purdue group are artifacts, resulting from their failure to correct the initial concentration for the material lost in the preceding peak. Finally, the residual Bi and T1 remaining at 1000°C seem to represent solid solutions in temperature-resistant phases, such as ‘Q’, the principal carrier of planetary noble gases in the meteorite.This distribution—a small amount in solid solution and a large amount in a surface film—qualitatively agrees with that predicted by Larimer (1973, Geochim. Cosmochim. Acta37, 1603–1623) for condensation from the solar nebula, though some of the substrates may have been sulfides rather than metal.Results for Abee and other primitive meteorites are essentially similar, except for a very abrupt 500°C release of T1 from Krymka (81%) and Bi from Tieschitz (70%). This release may represent decomposition of a thermolabile phase in a late condensate, such as organic matter or phyllosilicates. The presence of such a condensate (‘mysterite’) was inferred previously from the apparent overabundance of T1 and Bi in these meteorites.     

High‐accuracy practical spline‐based 3D and 2D integral transformations in potential‐field geophysics

Potential, potential field and potential‐field gradient data are supplemental to each other for resolving sources of interest in both exploration and solid Earth studies. We propose flexible high‐accuracy practical techniques to perform 3D and 2D integral transformations from potential field components to potential and from potential‐field gradient components to potential field components in the space domain using cubic B‐splines. The spline techniques are applicable to either uniform or non‐uniform rectangular grids for the 3D case, and applicable to either regular or irregular grids for the 2D case. The spline‐based indefinite integrations can be computed at any point in the computational domain. In our synthetic 3D gravity and magnetic transformation examples, we show that the spline techniques are substantially more accurate than the Fourier transform techniques, and demonstrate that harmonicity is confirmed substantially better for the spline method than the Fourier transform method and that spline‐based integration and differentiation are invertible. The cost of the increase in accuracy is an increase in computing time. Our real data examples of 3D transformations show that the spline‐based results agree substantially better or better with the observed data than do the Fourier‐based results. The spline techniques would therefore be very useful for data quality control through comparisons of the computed and observed components. If certain desired components of the potential field or gradient data are not measured, they can be obtained using the spline‐based transformations as alternatives to the Fourier transform techniques.     

NMR Logging to Estimate Hydraulic Conductivity in Unconsolidated Aquifers

Nuclear magnetic resonance (NMR) logging provides a new means of estimating the hydraulic conductivity (K) of unconsolidated aquifers. The estimation of K from the measured NMR parameters can be performed using the Schlumberger‐Doll Research (SDR) equation, which is based on the Kozeny–Carman equation and initially developed for obtaining permeability from NMR logging in petroleum reservoirs. The SDR equation includes empirically determined constants. Decades of research for petroleum applications have resulted in standard values for these constants that can provide accurate estimates of permeability in consolidated formations. The question we asked: Can standard values for the constants be defined for hydrogeologic applications that would yield accurate estimates of K in unconsolidated aquifers? Working at 10 locations at three field sites in Kansas and Washington, USA, we acquired NMR and K data using direct‐push methods over a 10‐ to 20‐m depth interval in the shallow subsurface. Analysis of pairs of NMR and K data revealed that we could dramatically improve K estimates by replacing the standard petroleum constants with new constants, optimal for estimating K in the unconsolidated materials at the field sites. Most significant was the finding that there was little change in the SDR constants between sites. This suggests that we can define a new set of constants that can be used to obtain high resolution, cost‐effective estimates of K from NMR logging in unconsolidated aquifers. This significant result has the potential to change dramatically the approach to determining K for hydrogeologic applications.