Magnitude of latent heat in thermally loaded clays

Temperature changes are known to induce specific couplings in clay, in particular, an anomalously high thermal pressurization in undrained conditions or a thermal compaction in drained conditions, both of which are potential threats for the mechanical stability and sealing capacity of the geomaterials. Thermodynamical analysis of those peculiar thermomechanical couplings points to a potentially important latent energy, which in turn could limit the temperature change upon heating or cooling. The direct measurement of latent energy developed during a laboratory geomechanical test is challenging. Instead, proper identification of thermal hardening in conventional experiments with temperature changes provides an alternative route to estimate latent energy. In this work, existing laboratory thermomechanical tests of clays are analyzed with a rigorous thermodynamic framework to quantify the magnitude of latent energy in thermomechanically loaded clays. A thermodynamically consistent constitutive model for fully saturated clays that combines two key features, (a) the temperature dependence of the blocked energy and (b) the framework of bounding plasticity, is proposed. The performance of the model is validated by reproducing results obtained in laboratory tests for Boom and Opalinus clays. The thermomechanical loads considered to validate the model performance were then used to estimate the percentage of work that remains latent in the clayey material during plastic yielding. We find that the magnitude of latent energy is quite significant, typically a few tens of percent of the total dissipated energy, and increases significantly with temperature. Accordingly, it is expected to play an important role in the thermomechanical response of clays.     

Effect of alpha-damage annealing on apatite (U–Th)/He thermochronology

Recent data on He diffusion challenge the temperature sensitivity of apatite (U–Th)/He thermochronology: the damage induced by recoil of U and Th decay series during emission of α particles (α-recoil damage) has been proposed to modify He-diffusion properties through time. However, we propose that annealing of these irradiation defects may be an important phenomenon and may be significant in case of slowly-cooled or reheated basement rocks. To test this hypothesis, we developed a quantitative model including an explicit treatment of α-recoil damage, annealing, and their effect on He-diffusion kinetics, and calibrate it against literature data. Our model is based on two hypotheses: (1) helium is in equilibrium between an apatite crystal and its defects and (2) alpha-recoil damage annealing can be described analogously to fission-track annealing. This model has been embedded into a Monte Carlo simulation of helium production/ejection/diffusion and applied to data from the French Massif Central; a complex slowly-cooled terrain with burial reheating, where the thermal history has been constrained by previous fission-track (FT) data including FT length distributions. (U–Th)/He ages are close to the FT ages from the same samples and are generally reproducible among replicates, but some samples present He-age dispersion that is not correlated with crystal size. Our model reproduces the Massif Central data very well except for three samples where He ages are older than corresponding FT ages. We show that annealing of irradiation damage has an important impact on retentivity of helium and that the He content, [He] is only a rough approximation of the damage level. In particular our results show that independence of He ages on crystal sizes, in case of reheated samples, is a clear indication of the higher He retentivity induced by α-recoil defects and that an explicit treatment of defect annealing is required for a correct interpretation of (U–Th)/He ages in such a case. More generally a correlation with the crystal size can bring information on the thermal path only if the age of defects, well represented by the fission-track age, is available, due to the dependence of the partial retention zone on damages. Conversely, in case of rapid cooling or for samples having low U and Th contents, damage effects can be ignored without significant effects on He ages.     

Garnet reequilibration and growth in the eclogite facies and geodynamical evolution near peak metamorphic conditions

Caledonian eclogite-facies metamorphism partially reworking Grenvillian granulite-facies anorthosite allows us to study the processes of garnet reequilibration at high pressure and to reconstruct the evolution of the unit near metamorphic peak conditions. Our results indicate that eclogite-facies metamorphism happened in two successive phases: first, inherited granulitic garnet was fractured and reequilibrated from their boundaries (crystal or fracture rims); then eclogite-facies minerals were crystallised in the fractures as overgrowths on inherited garnets. The reequilibration of inherited garnets is achieved through Fe²⁺Mg⁻¹ exchange, whereas eclogite-facies garnets crystallised during the subsequent phase are notably richer in Ca than un- and re-equilibrated granulitic garnet. Pseudosection construction shows that this lack in Ca reequilibration cannot be related to variations in thermodynamic conditions (a _H2O, reacting system composition) between the two phases. From the compilation of the available data, the reequilibration of granulitic garnet seems to be controlled by the inefficient intra- and inter-granular transport properties of Ca compared to Fe²⁺ and Mg. While these kinetic factors confine garnet reequilibration to Fe²⁺Mg⁻¹ exchange, the extent of reequilibration along this exchange vector is controlled by partitioning with adjacent omphacite. On the contrary to the diffusional reequilibration of granulitic garnet that lasted for several My according to our modelling of the diffusional relaxation, the strong compositional gradients between eclogite-facies and reequilibrated garnets, which are almost unaffected by diffusional reequilibration, provide evidence that rapid exhumation followed the crystallisation of eclogite-facies minerals. We propose that the movement reversal itself, from burial to exhumation, and associated deformation and fluid flow, triggered this crystallisation event. The resulting evolution near metamorphic peak conditions is therefore strongly asymmetrical: on the one hand, the prograde diffusional relaxation profiles indicate slow movement during the last stages of burial, whereas the unaffected retrograde overgrowth indicates fast exhumation rates.     

Statistical forecast of the marine surge

Natural Hazards - This paper studies different machine learning methods for solving the regression problem of estimating the marine surge value given meteorological data. The marine surge is...     

Nitrogen isotopes in the recent solar wind from the analysis of Genesis targets: Evidence for large scale isotope heterogeneity in the early solar system

We have analyzed nitrogen, neon and argon abundances and isotopic ratios in target material exposed in space for 27 months to solar wind (SW) irradiation during the Genesis mission. SW ions were extracted by sequential UV (193 nm) laser ablation of gold-plated material, purified separately in a dedicated line, and analyzed by gas source static mass spectrometry. We analyzed gold-covered stainless steel pieces from the Concentrator, a device that concentrated SW ions by a factor of up to 50. Despite extensive terrestrial N contamination, we could identify a non-terrestrial, ¹⁵N-depleted nitrogen end-member that points to a 40% depletion of ¹⁵N in solar-wind N relative to inner planets and meteorites, and define a composition for the present-day Sun (¹⁵N/¹⁴N = [2.26 ± 0.67] × 10⁻³, 2σ), which is indistinguishable from that of Jupiter’s atmosphere. These results indicate that the isotopic composition of nitrogen in the outer convective zone of the Sun has not changed through time, and is representative of the protosolar nebula. Large ¹⁵N enrichments due to e.g., irradiation, low temperature isotopic exchange, or contributions from ¹⁵N-rich presolar components, are therefore required to account for inner planet values.     

Solving 3D boundary element problems using constrained iterative approach

Some major challenges for geophysicists and structural geologists using three-dimensional boundary element method codes (3D-BEM) are: (1) reducing the amount of memory required to solve large and dense systems and (2) incorporation of inequality constraints such as traction inequality constraints (TIC) and displacement inequality constraints (DIC). The latter serves two purposes. First, for example, inequality constraints can be used to simulate frictional slip (using TIC). Second, these constraints can prevent element interpenetration while allowing opening mode (using DIC). We have developed a method that simultaneously incorporates both types of functionality of the inequality constraints. We show that the use of an appropriate iterative solver not only avoids the allocation of significant memory for solving the system (allowing very large model computation and simplifying parallelization on multi-core processors), but also admits interesting features such as natural incorporation of TICs and DICs. Compared to other techniques of contact management (e.g., Lagrange multipliers, penalty method, or complementarity problem), this new simple methodology, which does not use any incremental trial-and-error procedures, brings more flexibility, while making the system more stable and less subject to round-off errors without any computational overhead. We provide validations and comparisons of the inequality constraints implementation using 2D analytical and numerical solutions.     

A chemical and thermodynamic model of oil generation in hydrocarbon source rocks

Thermodynamic calculations and Gibbs free energy minimization computer experiments strongly support the hypothesis that kerogen maturation and oil generation are inevitable consequences of oxidation/reduction disproportionation reactions caused by prograde metamorphism of hydrocarbon source rocks with increasing depth of burial.These experiments indicate that oxygen and hydrogen are conserved in the process.Accordingly, if water is stable and present in the source rock at temperatures ?25 but ?100 °C along a typical US Gulf Coast geotherm, immature (reduced) kerogen with a given atomic hydrogen to carbon ratio (H/C) melts incongruently with increasing temperature and depth of burial to produce a metastable equilibrium phase assemblage consisting of naphthenic/biomarker-rich crude oil, a type-II/III kerogen with an atomic hydrogen/carbon ratio (H/C) of ∼1, and water. Hence, this incongruent melting process promotes diagenetic reaction of detritus in the source rock to form authigenic mineral assemblages.However, in the water-absent region of the system CHO (which is extensive), any water initially present or subsequently entering the source rock is consumed by reaction with the most mature kerogen with the lowest H/C it encounters to form CO₂ gas and a new kerogen with higher H/C and O/C, both of which are in metastable equilibrium with one another.This hydrolytic disproportionation process progressively increases both the concentration of the solute in the aqueous phase, and the oil generation potential of the source rock; i.e., the new kerogen can then produce more crude oil.Petroleum is generated with increasing temperature and depth of burial of hydrocarbon source rocks in which water is not stable in the system CHO by a series of irreversible disproportionation reactions in which kerogens with higher (H/C)s melt incongruently to produce metastable equilibrium assemblages consisting of crude oil, CO₂ gas, and a more mature (oxidized) kerogen with a lower H/C which in turn melts incongruently with further burial to produce more crude oil, CO₂ gas, and a kerogen with a lower H/C and so forth.The petroleum generated in the process progresses from heavy naphthenic crude oils at low temperatures to mature petroleum at ∼150 °C. For example, the results of Computer Experiment 27 (see below) indicate that the overall incongruent melting reaction in the water-absent region of the system C-H-O at 150 °C and a depth of ∼4.3 km of an immature type-II/III kerogen with a bulk composition represented by C₂₉₂H₂₈₈O_12(c) to produce a mature (oxidized) kerogen represented by C₁₂₈H₆₈O_7(c), together with a typical crude oil with an average metastable equilibrium composition corresponding to C_8.8H_16.9 (C_8.8H_16.9(l)) and CO₂ gas (CO_2(g)) can be described by writing

(A)     

Arsenic mobility in the ambient sulfidic environment: Sorption of arsenic(V) and arsenic(III) onto disordered mackinawite

Arsenate, As(V), sorption onto synthetic iron(II) monosulfide, disordered mackinawite (FeS), is fast. As(V) sorption decreases above the point of zero surface charge of FeS and follows the pH-dependent concentration of positively charged surface species. No redox reaction is observed between the As(V) ions and the mineral surface over the time span of the experiments. This observation shows that As(V) dominantly forms an outer-sphere complex at the surface of mackinawite. Arsenite, As(III), sorption is not strongly pH-dependent and can be expressed by a Freundlich isotherm. Sorption is fast, although slower than that of As(V). As(III) also forms an outer-sphere complex at the surface of mackinawite. In agreement with previous spectroscopic studies, complexation at low As(V) and As(III) concentration occurs preferentially at the mono-coordinated sulfide edge sites. The K_d (L g⁻¹) values obtained from linear fits to the isotherm data are ∼9 for As(V) and ∼2 for As(III). Stronger sorption of As(V) than As(III), and thus a higher As(III) mobility, may be reflected in natural anoxic sulfidic waters when disordered mackinawite controls arsenic mobility.