Thermal expansivities of supercooled haplobasaltic liquids

The thermal expansion of supercooled liquids in the haplobasaltic (anorthite-diopside) system have been determined via methods of container-based dilatometry. The expansivity data obtained in this study agree well with estimates provided by previous dilatometric determinations in the system that have relied on alternative experimental strategies. The data have been combined with high-temperature, superliquidus determinations of melt density to obtain expressions for the volume-temperature (V-T) relationships of liquids in the anorthite-diopside system. The V-T data clearly indicate a nonlinear temperature dependence of volume for all melts investigated. The variation is most striking for diopside, where the coefficient of volume thermal expansion decreases ∼56% from temperatures near the glass transition to superliquidus temperatures. With increasing anorthite content, the degree of variation appears to decrease. An₄₂Di₅₈ exhibits a decrease of 39% of its coefficient of thermal expansion and An₉₈Di₀₂ of 33%, respectively. The expansivities obtained in this study cannot be reproduced by means of published models that are based on linear V-T relationships. They require instead a reanalysis of existing pressure-V-T equations of state models for silicate melts.     

Deflation during caldera unrest: constraints on subsurface processes and hazard prediction from gravity–height data

We have evaluated published gravity-height ((g/(h) data on Campi Flegrei, Kilauea, Askja and Krafla, in order to discriminate between subsurface processes during caldera subsidence. With respect to end member gravity-height correlations, such as the free air gradient (FAG) and the Bouguer corrected free air (BCFAG), (g/(h gradients must be interpreted in terms of subsurface mass redistribution, density changes or some combination of these. (g/(h gradients during subsidence plot (1) along or below the BCFAG, (2) between the BCFAG and the FAG or (3) along or above the FAG. We have evaluated each of these three regions in terms of subsurface processes during volcano subsidence. We have interpreted (g/(h gradients as possible indicators of precursors of volcanic activity and propose that gravity-height surveys may help to detect precursors of caldera collapse caused by magma drainage. In this context, the 1875 eruption of Askja in Iceland has been re-interpreted in terms of the beginning of the eruptive episode being induced by roof collapse of an evacuating magma chamber. Based on other examples of recent volcanic roof collapses, we evaluate the contribution of gravity-height surveys in assessing volcanic risks during caldera subsidence. Caldera-forming eruptions are environmentally and economically the most devastating volcanic events. Inflation is usually considered to be an important precursor to activity. Here, we show that deflation may be associated with the trigger mechanism for caldera-forming explosive eruptions.     

Accuracy assessment of digital elevation models by means of robust statistical methods

Measures for the accuracy assessment of Digital Elevation Models (DEMs) are discussed and characteristics of DEMs derived from laser scanning and automated photogrammetry are presented. Such DEMs are very dense and relatively accurate in open terrain. Built-up and wooded areas, however, need automated filtering and classification in order to generate terrain (bare earth) data when Digital Terrain Models (DTMs) have to be produced. Automated processing of the raw data is not always successful. Systematic errors and many outliers at both methods (laser scanning and digital photogrammetry) may therefore be present in the data sets. We discuss requirements for the reference data with respect to accuracy and propose robust statistical methods as accuracy measures. Their use is illustrated by application at four practical examples. It is concluded that measures such as median, normalized median absolute deviation, and sample quantiles should be used in the accuracy assessment of such DEMs. Furthermore, the question is discussed how large a sample size is needed in order to obtain sufficiently precise estimates of the new accuracy measures and relevant formulae are presented.     

Protein carbonyls and antioxidant defenses in corkwing wrasse (Symphodus melops) from a heavy metal polluted and a PAH polluted site

The use of fish in environmental monitoring has become increasingly important in recent years as anthropogenic substances, many of which function as prooxidants, are accumulating in aquatic environments. We have measured a battery of antioxidant defenses as a measure of oxidative status, as well as protein carbonylation as a measure of oxidative damage, in corkwing wrasse (Symphodus melops) captured near a disused copper mine, where water and sediment are contaminated with heavy metals, and an aluminum smelter, a site contaminated with PAHs. Results were compared to two different reference sites. Fish at the heavy metal site had lower glucose-6-phosphate dehydrogenase activity and elevated protein carbonyls (1.8 times) compared to fish from the reference site. At the PAH site, EROD was increased 2-fold, while total glutathione and methemoglobin reductase concentration, were decreased. No differences were seen in protein carbonyl levels at the PAH site. Measures of both antioxidant defenses and oxidative damage should be used when assessing effects of xenobiotics on oxidative stress in fish species.     

Provenance of the Bosnian Flysch

Sandwiched between the Adriatic Carbonate Platform and the Dinaride Ophiolite Zone, the Bosnian Flysch forms a c. 3000 m thick, intensely folded stack of Upper Jurassic to Cretaceous mixed carbonate and siliciclastic sediments in the Dinarides. New petrographic, heavy mineral, zircon U/Pb and fission-track data as well as biostratigraphic evidence allow us to reconstruct the palaeogeology of the source areas of the Bosnian Flysch basin in late Mesozoic times. Middle Jurassic intraoceanic subduction of the Neotethys was shortly followed by exhumation of the overriding oceanic plate. Trench sedimentation was controlled by a dual sediment supply from the sub-ophiolitic high-grade metamorphic soles and from the distal continental margin of the Adriatic plate. Following obduction onto Adria, from the Jurassic–Cretaceous transition onwards a vast clastic wedge (Vranduk Formation) was developed in front of the leading edge, fed by continental basement units of Adria that experienced Early Cretaceous synsedimentary cooling, by the overlying ophiolitic thrust sheets and by redeposited elements of coeval Urgonian facies reefs grown on the thrust wedge complex. Following mid-Cretaceous deformation and thermal overprint of the Vranduk Formation, the depozone migrated further towards SW and received increasing amounts of redeposited carbonate detritus released from the Adriatic Carbonate Platform margin (Ugar Formation). Subordinate siliciclastic source components indicate changing source rocks on the upper plate, with ophiolites becoming subordinate. The zone of the continental basement previously affected by the Late Jurassic–Early Cretaceous thermal imprint has been removed; instead, the basement mostly supplied detritus with a wide range of pre-Jurassic cooling ages. However, a c. 80 Ma, largely synsedimentary cooling event is also recorded by the Ugar Formation, that contrasts the predominantly Early Cretaceous cooling of the Adriatic basement and suggests, at least locally, a fast exhumation.     

Impacts of Methane on Carbon Dioxide Storage in Brine Formations

In the context of geological carbon sequestration (GCS), carbon dioxide (CO₂) is often injected into deep formations saturated with a brine that may contain dissolved light hydrocarbons, such as methane (CH₄). In this multicomponent multiphase displacement process, CO₂ competes with CH₄ in terms of dissolution, and CH₄ tends to exsolve from the aqueous into a gaseous phase. Because CH₄ has a lower viscosity than injected CO₂, CH₄ is swept up into a ‘bank’ of CH₄‐rich gas ahead of the CO₂ displacement front. On the one hand, this may provide a useful tracer signal of an approaching CO₂ front. On the other hand, the emergence of gaseous CH₄ is undesirable because it poses a leakage risk of a far more potent greenhouse gas than CO₂ if the cap rock is compromised. Open fractures or faults and wells could result in CH₄ contamination of overlying groundwater aquifers as well as surface emissions. We investigate this process through detailed numerical simulations for a large‐scale GCS pilot project (near Cranfield, Mississippi) for which a rich set of field data is available. An accurate cubic‐plus‐association equation‐of‐state is used to describe the non‐linear phase behavior of multiphase brine‐CH₄‐CO₂ mixtures, and breakthrough curves in two observation wells are used to constrain transport processes. Both field data and simulations indeed show the development of an extensive plume of CH₄‐rich (up to 90 mol%) gas as a consequence of CO₂ injection, with important implications for the risk assessment of future GCS projects.