Progress and new directions in high temperature calorimetry revisited

 High temperature reaction calorimetry has seen considerable advances over the past twenty years. New and more sensitive calorimeters, improved sample handling techniques, and better control of the final dissolved state has made solution calorimetry and drop solution calorimetry, using molten lead borate and other solvents, very versatile and reliable techniques. This paper summarizes these advances and presents examples of specific applications to problems of transition metal oxide chemistry, high pressure geophysics, melt and glass energetics, and metastable materials relevant to the earth sciences. Received June 3, 1996 / Revised, accepted Spetember 23, 1996     

Intrinsic groundwater vulnerability determination at the aquifer scale: a methodology coupling travel time estimation and rating methods

Groundwater vulnerability has been subject of much research due to the valuable information it provides concerning groundwater protection and exploitation potential. Up to now, most groundwater vulnerability studies adopt subjective systems of rating the various factors and subsequently, their results are often ambiguous and contradicting. Within the present study a methodology for the estimation of intrinsic groundwater vulnerability at the aquifer scale is presented. The methodology is based on travel time estimation from specified sources of pollution to the aquifer. Besides the deterministic calculation of travel times, the methodology provides a rating system for each pollution source, based on its relative severity and the estimated threat that it poses to the aquifer. Therefore, it can be regarded as a hybrid method that couples the advantages provided by the physically based methods with those of the subjective rating systems. The methodology is applied to the Neon Sidirochorion aquifer, Northeastern Greece, an overexploited aquifer where river waters, sea waters and lake waters interact, causing groundwater quality deterioration to the aquifer. The results indicated that the proposed groundwater vulnerability assessment methodology is well capturing pollution related to saltwater intrusion and agricultural activities, while it is concluded that the conceptual model is significantly affecting the vulnerability assessment results and therefore has to be previously developed.     

Electrodialytic remediation of CCA-treated waste wood in pilot scale

When chromated copper arsenate (CCA)-treated wood is removed from service and turns into waste, the contents of Cu, Cr and As remain high due to the strong fixation of CCA in the wood. This high content of toxic compounds presents a disposal challenge. Incineration of CCA-treated waste wood is not allowed in Denmark; instead, the wood is to be land-filled until new methods for handling the wood are available. Since the amounts of CCA-treated wood being removed from service is expected to increase in the years to come, the need for finding alternative handling methods is very relevant. In this study, the usefulness of Electrodialytic Remediation was demonstrated for handling of CCA-treated waste wood in pilot scale. The electrodialytic remediation method, which uses a low-level direct current (DC) as the cleaning agent, combines electrokinetic movement of ions in the wood matrix with the principles of electrodialysis. It has previously been shown that it is possible to remove Cu, Cr and As from CCA-treated wood using electrodialytic remediation in laboratory scale, but until now, the method had not been studied in large scale. The pilot-scale plant used in this study was designed to contain up to 2 m³ wood chips. Six remediation experiments were carried out. In these experiments, the process was up-scaled stepwise by increasing the distance between the electrodes from initially 60 cm to finally 150 cm. The remediation time was varied between 11 and 21 days, and phosphoric acid and/or oxalic acid was used to facilitate the desorption of CCA from the wood. In the most successful of the experiments carried out, the concentration of CCA in the wood was reduced by up to 82% for Cr, 88% for Cu and at least 96% for As.     

Grid Refinement in Cartesian Coordinates for Groundwater Flow Models Using the Divergence Theorem and Taylor's Series

Grid refinement is introduced in a numerical groundwater model to increase the accuracy of the solution over local areas without compromising the run time of the model. Numerical methods developed for grid refinement suffered certain drawbacks, for example, deficiencies in the implemented interpolation technique; the non‐reciprocity in head calculations or flow calculations; lack of accuracy resulting from high truncation errors, and numerical problems resulting from the construction of elongated meshes. A refinement scheme based on the divergence theorem and Taylor's expansions is presented in this article. This scheme is based on the work of De Marsily (1986) but includes more terms of the Taylor's series to improve the numerical solution. In this scheme, flow reciprocity is maintained and high order of refinement was achievable. The new numerical method is applied to simulate groundwater flows in homogeneous and heterogeneous confined aquifers. It produced results with acceptable degrees of accuracy. This method shows the potential for its application to solving groundwater heads over nested meshes with irregular shapes.     

Derivation Of Refractive Index And Temperature Gradients From Optical Scintillometry To Correct Atmospherically Induced Errors For Highly Precise Geodetic Measurements

Refraction effects of optical beams are generally caused by an inhomogeneous propagation medium and are a major source of systematic errors in the precise optical determination of angles and distances in the atmospheric surface layer. In this contribution a method for deriving vertical temperature and refractive index gradients from optical scintillation is presented. Knowledge of these gradients is required for the compensation of atmospherically induced errors for highly precise terrestrial geodetic measurements, like direct transfer and levelling. The advantage of the present optical method is, that temperature and refractive index gradients can be derived as line-averaged values over the propagation path, which is not possible by meteorological point measurements. Field observations have been carried out with a displaced-beam scintillometer over flat terrain and under different atmospheric conditions in order to verify this method. The experiments show, that this method allows to derive accurate correction values for precise terrestrial geodetic measurements.     

Direct measurements of latent heat during crystallization and melting of a ugandite and an olivine basalt

Step-scanning calorimetric measurements using a Setaram HT1500 calorimeter were performed between 800 and 1400°C on two natural samples: a ugandite from the East African rift and an olivine basalt from the western Mexican arc. Our measurements provide the first in-situ quantitative assessment of enthalpy during melting of initially crystalline natural samples. The distribution of latent heat across the liquidus-solidus intervals of the two samples is distinctly different, reflecting significant variation in the sequence and abundance of mineral phases during melting (clinopyroxene and leucite in the ugandite; olivine, clinopyroxene, and plagioclase in the basalt). Our data further indicate that the common assumption of a uniform distribution of latent heat across the liquidus-solidus interval of a magma is a reasonable approximation for the olivine basalt, but is grossly in error for the ugandite. This is due to cotectic precipitation of leucite and clinopyroxene, leading to a large, disproportionate release of latent heat early in the crystallization sequence. The implication for the thermal history of a crystallizing ugandite magma is that therate of heat loss during conductive cooling will unitially be more rapid than the average rate. The net result will be to produce lower magmatic temperatures after a given cooling interval relative to models assuming a uniform release of latent heat. An additional series of scanning calorimetric experiments were performed at variable rates (1,2 and 3°/min) to evaluate the role of kinetics on the distribution of enthalpy during both melting and crystallization of the ugandite and olivine basalt. The results indicate that clinopyroxene is the most important mineral phase in controlling the shapes of the enthalpy profiles during cooling; this is due to its large enthalpy of fusion and its tendency for sluggish nucleation, followed by rapid crystallization at temperatures that vary with cooling rate. The resolution of the calorimeter (in terms of heat detected per unit time) is also important in determining the shapes of theobserved enthalpy profiles during these rapid scans. Estimates based on the observed calorimetric signal associated with melting of olivine, and the lack of a calorimetric signal during melting of leucite, combined with known enthalpies of fusion for the two phases, indicate detection limits of approximately 0.6–1.2 kJ per 5 min increments.     

Palynological and geochemical response to environmental changes in the Lower Cretaceous in the Outer Western Carpathians; a record from the Silesian unit, Czech Republic

Rich dinoflagellate cyst assemblages recorded from the Vendryne Formation, Tesin Limestone, and Hradiste Formation of the Silesian unit, Czech Republic are presented. The results of a qualitative and quantitative study of dinoflagellate cysts are presented and discussed. Age-assessment of the sediments based on 86 species suggests a Late Tithonian to Early Berriasian age for the Vendryne Formation and a Late Berriasian (Otopeta Ammonite Zone) to the basal part of the Late Valanginian (Verrucosum Ammonite Zone) age for the Tesin Limestone. Pelitic flyschoid sediments of the Hradiste Formation belong to the Late Valanginian - Early Hauterivian age. Quantitative palynological study and carbon isotope analysis were applied to understand the change from the grey clays to dark grey clays sedimentation. The dinoflagellate cyst assemblages show deposition in a shallow-sea environment. An increasing amount of sporomorphs towards the overlying layers (they are the most abundant in the Hradiste Formation) shows a growing supply of terrestrial material at the same time. The values of δ¹³C increased significantly from a level of 0.43 or 0.75-1.81‰ in the Late Valanginian. This change probably indicates an increase in organic matter storage and perturbation of the carbon cycle connected with the dark grey clays sedimentation.     

The Lemnos 8 January 2013 (M w = 5.7) earthquake: fault slip,aftershock properties and static stress transfer modeling in the north Aegean Sea

We investigate mainshock slip distribution and aftershock activity of the 8 January 2013 M _w?=?5.7 Lemnos earthquake, north Aegean Sea. We analyse the seismic waveforms to better understand the spatio-temporal characteristics of earthquake rupture within the seismogenic layer of the crust. Peak slip values range from 50 to 64 cm and mean slip values range from 10 to 12 cm. The slip patches of the event extend over an area of dimensions 16?×?16 km². We also relocate aftershock catalog locations to image seismic fault dimensions and test earthquake transfer models. The relocated events allowed us to identify the active faults in this area of the north Aegean Sea by locating two, NE–SW linear patterns of aftershocks. The aftershock distribution of the mainshock event clearly reveals a NE–SW striking fault about 40 km offshore Lemnos Island that extends from 2 km up to a depth of 14 km. After the mainshock most of the seismic activity migrated to the east and to the north of the hypocenter due to (a) rupture directivity towards the NE and (b) Coulomb stress transfer. A stress inversion analysis based on 14 focal mechanisms of aftershocks showed that the maximum horizontal stress is compressional at N84°E. The static stress transfer analysis for all post-1943 major events in the North Aegean shows no evidence for triggering of the 2013 event. We suggest that the 2013 event occurred due to tectonic loading of the North Aegean crust.