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.     

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.     

Numerical modelling of stream–aquifer interaction: Quantifying the impact of transient streambed permeability and aquifer heterogeneity

Stream–aquifer interaction plays a vital role in the water cycle, and a proper study of this interaction is needed for understanding groundwater recharge, contaminants migration, and for managing surface water and groundwater resources. A model‐based investigation of a field experiment in a riparian zone of the Schwarzbach river, a tributary of the Rhine River in Germany, was conducted to understand stream–aquifer interaction under alternative gaining and losing streamflow conditions. An equivalent streambed permeability, estimated by inverting aquifer responses to flood waves, shows that streambed permeability increased during infiltration of stream water to aquifer and decreased during exfiltration. Aquifer permeability realizations generated by multiple‐point geostatistics exhibit a high degree of heterogeneity and anisotropy. A coupled surface water groundwater flow model was developed incorporating the time‐varying streambed permeability and heterogeneous aquifer permeability realizations. The model was able to reproduce varying pressure heads at two observation wells near the stream over a period of 55 days. A Monte Carlo analysis was also carried out to simulate groundwater flow, its age distribution, and the release of a hypothetical wastewater plume into the aquifer from the stream. Results of this uncertainty analysis suggest (a) stream–aquifer exchange flux during the infiltration periods was constrained by aquifer permeability; (b) during exfiltration, this flux was constrained by the reduced streambed permeability; (c) the effect of temporally variable streambed permeability and aquifer heterogeneity were found important to improve the accurate capture of the uncertainty; and (d) probabilistic infiltration paths in the aquifer reveal that such pathways and the associated prediction of the extent of the contaminant plume are highly dependent on aquifer heterogeneity.     

Correction to: The contributions of fronts,lows and thunderstorms to southern Australian rainfall

Climate Dynamics - In the original published version of the paper, the figures reported in Sect. 4 relating the proportion of rainfall in southern Australia that is due to each of the...     

Deep Norden： Highlights of the lithospheric structure of Northern Europe, Iceland, and Greenland

We present a review of geophysical models of the continental lithosphere of Norden, which includes the Nordic countries （Denmark, Iceland, Finland, Norway, Sweden）, Greenland, and the adjacent regions of the neighbouring countries. The structure of the crust and the lithospheric mantle reflects the geologic evolution of Norden from Precambrian terrane accretion and subduction within the Baltic Shield and Greenland to Phanerozoic rifting, volcanism, magmatic crust formation, subduction and continent-continent collision at the edges of the cratons and at the plate boundaries. The proposed existence of a mantle plume below Iceland has not been uniquely demonstrated by the available seismic evidence. Its connection to the break-up of the North Atlantic Ocean c. 65 My ago is uncertain, but the 〉30 km thick crust in the strait between Iceland and Greenland may indicate the track of the plume. Using the results from seismic （reflection and refraction profiles, P- and S-wave, body-wave and surface-wave tomography）, thermal, gravity, and petrologic studies,we review the structure of the crust and the lithospheric mantle of Norden and propose an integrated model of physical properties of the lithosphere of the region, including maps of lateral variation in crustal and lithospheric thicknesses and compositional variation in the lithospheric mantle.     

Seismic expression of gas and gas hydrates across the western Black Sea

This study is a synthesis of gas-related features in recent sediments across the western Black Sea basin. The investigation is based on an extensive seismic dataset, and integrates published information from previous local studies. Our data reveal widespread occurrences of seismic facies indicating free gas in sediments and gas escape in the water column. The presence of gas hydrates is inferred from bottom-simulating reflections (BSRs). The distribution of the gas facies shows (1) major gas accumulations close to the seafloor in the coastal area and along the shelfbreak, (2) ubiquitous gas migration from the deeper subsurface on the shelf and (3) gas hydrate occurrences on the lower slope (below 750 m water depth). The coastal and shelfbreak shallow gas areas correspond to the highstand and lowstand depocentres, respectively. Gas in these areas most likely results from in situ degradation of biogenic methane, probably with a contribution of deep gas in the shelfbreak accumulation. On the western shelf, vertical gas migration appears to originate from a source of Eocene age or older and, in some cases, it is clearly related to known deep oil and gas fields. Gas release at the seafloor is abundant at water depths shallower than 725 m, which corresponds to the minimum theoretical depth for methane hydrate stability, but occurs only exceptionally at water depths where hydrates can form. As such, gas entering the hydrate stability field appears to form hydrates, acting as a buffer for gas migration towards the seafloor and subsequent escape.     

黑海复合型海底模拟反射层:古气候条件的潜在性指标

在多瑙河深海扇高分辨率反射地震资料中发现了以前鲜为人知的复合型海底模拟反射层(BSRs)模式,其声波特征显示与游离气有关.研究表明该模式与多瑙河扇独特的河道-堤岸系统结构有关.