A comparative study of the modelling of cement hydration and cement-rock laboratory experiments

The use of cement and concrete as fracture grouting or as tunnel seals in a geological disposal facility for radioactive wastes creates potential issues concerning chemical reactivity. From a long-term safety perspective, it is desirable to be able model these interactions and changes quantitatively. The ‘Long-term Cement Studies’ (LCS) project was formulated with an emphasis on in situ field experiments with more realistic boundary conditions and longer time scales compared with former experiments. As part of the project programme, a modelling inter-comparison has been conducted, involving the modelling of two experiments describing cement hydration on one hand and cement-rock reaction on the other, with teams representing the NDA (UK), Posiva (Finland), and JAEA (Japan).This modelling exercise showed that the dominant reaction pathways in the two experiments are fairly well understood and are consistent between the different modelling teams, although significant differences existed amongst the precise parameterisation (e.g. reactive surface areas, dependences of rate upon pH, types of secondary minerals), and in some instances, processes (e.g. partition of alkali elements between solids and liquid during cement hydration; kinetic models of cement hydration). It was not conclusive if certain processes such as surface complexation (preferred by some modellers, but not by others) played a role in the cement-rock experiment or not. These processes appear to be more relevant at early times in the experiment and the evolution at longer timescales was not affected. The observed permeability profile with time could not be matched. The fact that no secondary minerals could be observed and that the precipitated mass calculated during the simulations is minor might suggest that the permeability reduction does not have a chemical origin, although a small amount of precipitates at pore throats could have a large impact on permeability.The modelling exercises showed that there is an interest in keeping the numerical models as simple as possible and trying to obtain a reasonable fit with a minimum of processes, minerals and parameters. However, up-scaling processes and model parameterisation to the timescales appropriate to repository safety assessment are of considerable concern. Future modelling exercises of this type should focus on a suitable natural or industrial analogue that might aid assessing mineral-fluid reactions at these longer timescales.     

B and Li isotopes as intrinsic tracers for injection tests in aquifer storage and recovery systems

Boron and Li isotopes have been tested as environmental tracers of treated sewage injected into a sandy aquifer (Shafdan reclamation project, Israel). During a 38 days injection test in a newly dug injection well, a conservative artificial tracer (Br⁻) was monitored together with δ¹¹B and δ⁷Li in the injectate, in the unsaturated soil zone (porous cup) and an observation well in the aquifer. In spite of B and Li concentrations in the injectate close to background values, significant shifts of the isotope signatures could be observed over the duration of the injection test. Boron isotope ratios show a breakthrough curve delayed with respect to Br⁻ breakthrough due to some reversible sorption on the aquifer material. No isotope fractionation was observed in the unsaturated or the saturated zone so that B isotopes can be considered as conservative in the investigated part of the aquifer system. Lithium isotopes are strongly fractionated, probably due to sorption processes. Lithium concentrations point to a Li sink in the system, δ⁷Li values vary strongly with a tendency of ⁷Li depletion in the liquid phase over the duration of the experiment. This is opposite to the expected preferential sorption of ⁶Li onto clay minerals. Boron isotopes reveals a valuable tracer of artificial recharge of freshwaters derived from treated sewage, both for short term tracer tests and for long-term monitoring of artificial recharge, even if in aquifers with higher clay contents, sorption-linked isotope fractionation cannot be excluded. More data are needed on Li isotope fractionation in natural groundwater systems to assess the potential of this tracer as monitoring tool.     

Seismotectonic models and CN algorithm: The case of Italy

The CN algorithm is utilized here both for the intermediate term earthquake prediction and to validate the seismotectonic model of the Italian territory. Using the results of the analysis, made through the CN algorithm and taking into account the seismotectonic model, three main areas, one for Northern Italy, one for Central Italy and one for Southern Italy, are defined. Two transition areas between the three main areas are delineated. The earthquakes which occurred in these two areas contribute to the precursor phenomena identified by the CN algorithm in each main area.     

Transient Electric Field in the Mesosphere above a Γ-shape Lightning Stroke

We describe the space–time distribution of the pulsed electric field in the middle atmosphere above a positive Γ-shaped lightning stroke. The channel of such a discharge contains a vertical and a horizontal section. The current wave moves initially vertically and then turns horizontally so that radiation appears from the vertical electric dipole followed by that from the horizontal dipole. Combined with reflection from the perfectly conducting ground, the source provides three subsequent pulses in the atmosphere, with the lag being determined by the finite velocity of the current wave in the Γ-shaped stroke. The pulses are reproduced by reflections from the air-ground and the air-ionosphere interfaces and the waveform resembles the M-component, which is often noted in the negative strokes (e.g. Yashunin et al., J Geophys Res 112:D10109, 2007). The non-stationary fine structure appears in the spatial distribution of electric field, which persists for 2 ms or even more and exceeds the runaway electron threshold. Estimates support the idea of free electron bunching in the mesosphere by the pulsed electric field. Focusing may occur about 10 km away from the point of electron- field interaction; it is delayed by a few ms from the moment of interaction. The data presented might be helpful in realistic modeling of the red sprite formation.     

The effects of visual realism,spatial abilities,and competition on performance in map-based route learning in men

We report on how visual realism might influence map-based route learning performance in a controlled laboratory experiment with 104 male participants in a competitive context. Using animations of a dot moving through routes of interest, we find that participants recall the routes more accurately with abstract road maps than with more realistic satellite maps. We also find that, irrespective of visual realism, participants with higher spatial abilities (high-spatial participants) are more accurate in memorizing map-based routes than participants with lower spatial abilities (low-spatial participants). On the other hand, added visual realism limits high-spatial participants in their route recall speed, while it seems not to influence the recall speed of low-spatial participants. Competition affects participants’ overall confidence positively, but does not affect their route recall performance neither in terms of accuracy nor speed. With this study, we provide further empirical evidence demonstrating that it is important to choose the appropriate map type considering task characteristics and spatial abilities. While satellite maps might be perceived as more fun to use, or visually more attractive than road maps, they also require more cognitive resources for many map-based tasks, which is true even for high-spatial users.     

A subsidiary fast-diffusing substitution mechanism of Al in forsterite investigated using diffusion experiments under controlled thermodynamic conditions

Diffusion of Al in synthetic forsterite was studied at atmospheric pressure from 1100 to 1500 °C in air along [100] with activities of SiO₂, MgO and Al₂O₃ (a_SiO2, a_MgO and a_Al2O3) buffered. At low a_SiO2, the buffer was forsterite + spinel + periclase (fo + sp + per) at all temperatures, while at high a_SiO2 and subsolidus conditions a variety of three-phase assemblages containing forsterite and two other phases from spinel, cordierite, protoenstatite or sapphirine were used at 1100–1350 °C. Experiments at high a_SiO2 and 1400 °C used forsterite + protoenstatite + melt (fo + en + melt), and at 1500 °C, fo + melt. The resulting diffusion profiles were analysed by LA–ICP–MS in scanning mode. Diffusion profiles in the high a_SiO2 experiments were generally several hundred microns in length, but diffusion at low a_SiO2 was three orders of magnitude slower than in high a_SiO2 experiments carried out at the same temperature, producing short profiles only a few microns in length and close to the spatial resolution of the analytical method. Interface concentrations of Al in the forsterite, obtained by extrapolating the diffusion profiles to the crystal/buffer interface, were only a fraction of those expected at equilibrium, and varied among the differing buffer assemblages according to (a_Al2O3)^1/2 and (a_SiO2)^3/4, pointing to the substitution of Al in forsterite by an octahedral-site, vacancy-coupled (OSVC) component with the stoichiometry Al _4/3 ³⁺ vac_2/3SiO₄, whereas the main substitution expected from previous equilibrium studies would be the coupled substitution of 2 Al for Mg + Si, giving the stoichiometry MgAl₂O₄. It is proposed that this latter substitution is not seen on the length scales of the present experiments because it requires replacement of Si by Al on tetrahedral sites, and is accordingly rate-limited by the slow diffusivity of Si. Instead, diffusion of Al by the OSVC mechanism is relatively fast, and at high a_SiO2, even faster than Fe–Mg interdiffusion.     

Some results obtained on the study of the chemical composition of Eurasian oils depending on the depth and age of the reservoir rock

The sulfur, paraffin, resin and asphaltene contents of some 6570 Cenozoic, Mesozoic and Paleozoic Eurasian oils were analysed statistically in terms of reservoir age and depth. The database includes all principal oil-bearing basins from 60 Eurasian countries. The results of the studies of the relationships between the distribution of oils with different sulfur, paraffin, resin and asphaltene contents and the reservoir age and depth are presented. Predictive trends are established allowing polynomial predictions of average properties.     

Wave propagation in elastic media with stress-induced anisotropy

Summary. The effect of initial stress on the velocities of plane elastic waves is considered and corrections to the first order in terms of initial stress for P -and S -waves are obtained. The results are compared with those of Dahlen, who found that to the first order the initial stress had no effect on P -wave velocities: this conclusion is shown to be correct only when the unstressed material is isotropic.