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.     

Perturbed physics ensemble using the MIROC5 coupled atmosphere–ocean GCM without flux corrections: experimental design and results

In this study, we constructed a perturbed physics ensemble (PPE) for the MIROC5 coupled atmosphere–ocean general circulation model (CGCM) to investigate the parametric uncertainty of climate sensitivity (CS). Previous studies of PPEs have mainly used the atmosphere-slab ocean models. A few PPE studies using a CGCM applied flux corrections, because perturbations in parameters can lead to large radiation imbalances at the top of the atmosphere and climate drifts. We developed a method to prevent climate drifts in PPE experiments using the MIROC5 CGCM without flux corrections. We simultaneously swept 10 parameters in atmosphere and surface schemes. The range of CS (estimated from our 35 ensemble members) was not wide (2.2–3.2?°C). The shortwave cloud feedback related to changes in middle-level cloud albedo dominated the variations in the total feedback. We found three performance metrics for the present climate simulations of middle-level cloud albedo, precipitation, and ENSO amplitude that systematically relate to the variations in shortwave cloud feedback in this PPE.     

Effect of divalent cations on the kinetics of Fe(III) complexation by organic ligands in natural waters

We have investigated the kinetics of Fe(III) complexation by several organic ligands including fulvic acid, citrate and ethylenediaminetetraacetic acid (EDTA). Particular attention was given to examination of the effect of competitive divalent cations (Me: Ca²⁺ and Mg²⁺) at concentrations typical of seawater on the complexation rate. All experiments were conducted in 0.5 M NaCl solution buffered with 2 mM bicarbonate at pH 8.0 in the absence and presence of Me (25 μM-250 mM). The rate constants of complex formation determined by using the competitive ligand (5-sulfosalicylic acid) method combined with visible spectrophotometry ranged from 3.3 × 10⁴ to 3.2 × 10⁶ M⁻¹ s⁻¹. The mechanism of complexation was then examined based on a kinetic model. When EDTA was used as a ligand, Me at concentrations comparable to the ligand markedly retarded the rate of iron complex formation due to the predominance of an adjunctive pathway (where iron-ligand complex is formed via direct association of iron to Me-ligand complex). In contrast, the competing effect of Me on iron complexation by citrate and fulvic acid was observed only when the Me concentration was in excess of the ligand by more than a factor of 10-1000. The kinetic model suggests that iron complexation by fulvic acid occurs predominantly via a disjunctive pathway (where iron complexation by ligand occurs after dissociation of Me from Me-ligand complex) at concentrations of divalent cations and natural organic matter typical of natural waters including seawater and freshwater.     

Numerical study for specifying the major origin of low salinity water associated with <Emphasis Type="Italic">Chattonella</Emphasis> (Raphidophyceae) blooms in Tachibana Bay,Japan

In both 2009 and 2010, massive Chattonella blooms occurred in Tachibana Bay. Observation results show that high cell densities of Chattonella were distributed in the central area of Tachibana Bay with low salinity water. Model results indicate that the low salinity water originated from the Ariake Sea and intruded into Tachibana Bay during the northerly or weak winds. It is suggested that low salinity water was mainly discharged from the northern area of the Ariake Sea. Northerly wind enhanced the horizontal advection of the low salinity water intruding into Tachibana Bay originating from the northern area of the Ariake Sea.     

Seasonal Variability in Circulation Pattern and Residence Time of Suo-Nada

The development and evolution of the persistent counterclockwise circulation in Suo-Nada have been studied in detail using a three-dimensional numerical model. The realistic circulation has been reproduced from the monthly climatological fields of salinity, temperature along the open boundary, wind, heat flux and buoyancy input from twenty-two major rivers surrounding the basin. The seasonal variation of fresh-water discharge from the rivers proved to be the most important forcing mechanism driving the circulation. The expansion and contraction of coastal low salinity water well corresponded with the development of counterclockwise circulation from spring to summer and dissipation from autumn to winter. The circulation was found to be vertically homogenous and quasi-barotropic. However, confined along the coastal zone is an estuarine flow (i.e., oppositely directed currents in the upper and lower layers) whose horizontal dimension conforms to the period of maximum buoyancy flux from the rivers. This indicates that the flow pattern in Suo-Nada can be separated into two distinct regions where the relative dominance of estuarine circulation plays a significant role. Furthermore, the monthly water exchange capacity for autonomous purification of the basin has been evaluated from the average residence time of conservative material based on the calculated current field. It is demonstrated that the kinetic energy of the basin is directly responsible in promoting water exchange in Suo-Nada. This revised version was published online in August 2006 with corrections to the Cover Date.     

Intraannual variability of sea level around Tosa Bay

Through analysis of monthly in situ hydrographic, tide gauge, altimetry and Kuroshio axis data for the years 1993–2001, the intraannual variability of sea level around Tosa Bay, Japan, with periods of 2–12 months is examined together with the intraannual variability of the Kuroshio south of the bay. It is shown that the intraannual variation of steric height on the slope in Tosa Bay can account for that of sea level at the coast around the bay as well as on this slope. It is found that the steric height (or sea level) variation on the slope in this bay is mainly controlled by the subsurface thermal variation correlated with the Kuroshio variation off Cape Ashizuri, the western edge of Tosa Bay. That is, when the nearshore Kuroshio velocity south of the cape is intensified [weakened] concurrently with the northward [southward] displacement of the current axis, temperature in an entire water column decreases [increases] simultaneously, mainly due to the upward [downward] displacement of isotherms, coincident with that of the main thermocline. It follows that the steric height (or sea level) decreases [increases].     

Circulation and Material Transport in Suo-Nada during Spring and Summer

An attempt was made to reproduce the circulation pattern in Suo-Nada, Japan during spring and summer season in order to elucidate the water exchange mechanism in the basin. Two hydrographic surveys at the end of each season were conducted covering the entire Suo-Nada area. A three-dimensional hydrodynamic Princeton Ocean Model (POM) was used to compute the current resulting from the observed density and wind field. During spring, a very pronounced counter clockwise gyre is situated near the opening of the basin. This is replaced by a clockwise circulation which seemed to occupy the whole domain during summer. Within each season, however, the vertical distribution of current does not show any remarkable differences, indicating the dominance of horizontal current and a very weak estuarine flow. These observational and numerical results were used to estimate the remnant function and the corresponding average residence time of permanently dissolved matter (PDM) and transformable matter (TM). The results revealed a small difference in the average residence times of materials within each season but a large seasonal variability between spring and summer. Furthermore, calculations based on climatological density fields have indicated a similar trend of variation between the seasonal values of average residence times. This revised version was published online in July 2006 with corrections to the Cover Date.     

Numerical modelling of the three-dimensional stress field in southwestern Japan

It has been inferred from the focal mechanism of earthquakes and their hypocenter distribution (Shiono, 1977) that the stress field in southwestern Japan indicates complicated features; a NW-SE compression at shallow depths along the Nankai trough, an E-W or ESE-WNW compression in the inland crust, an extension parallel to the leading edge of the Philippine Sea plate at subcrustal depths in the region from the southern Chubu to northwestern Shikoku, and a down-dip tension beneath the Kyushu island.In order to investigate possible sources of these complex features of the stress state, a three-dimensional finite element method is employed to model the configuration of the subducting Philippine Sea plate, taking into consideration the following three possible types of forces:

1. (1) A negative buoyancy due to the density contrast between the subducting plate and the surrounding mantle.

2. (2) A northwestward compressive force generated by the movement of the Philippine Sea plate.

3. (3) A westward compressive force due to the movement of the Pacific plate.

For various combinations of different magnitudes of these forces, and of different elastic moduli, the stresses at a number of selected sites are calculated, and their directions are compared with those inferred from the focal mechanism and other geophysical information.It is found that the observed extensional stresses parallel to the leading edge of the subducting Philippine Sea plate may be caused mainly by the negative buoyancy. The northwestward compressive force may not play an important role in generating the complex stress field in southwestern Japan. The observed E-W compressional stress field prevailing in the inland region appears to result mainly from the westward-moving Pacific plate. The present results suggest that if a thin low-velocity transitional layer exists just above the subducting Philippine Sea plate, it could give appreciable effects on the mechanism of low-angled thrust faulting off the Kii peninsula and the Shikoku island.The magnitude of the shear stress in the continental crust and in the subducting plate is estimated to be of the order of several hundred bars, although the calculated shear stresses are considerably affected by the configuration of the subducting plate and also by the applied forces.It is interesting that the stress distribution appears to have some relations to seismicity of subcrustal earthquakes, and to the rupture process of large thrust earthquakes along the plate boundary.     

Sensitivity of the central Asian climate to uplift of the Tibetan Plateau in the coupled climate model (MRI-CGCM1)

Abstract   The relationship between the altitude of the Tibetan Plateau and climate change in central Asia was investigated through a numeric experiment using the Meteorological Research Institute (MRI) coupled atmosphere–ocean general circulation model I (MRI-CGCM1). The results suggest that summer precipitation in central Asia decreased significantly as the Tibetan Plateau rose in height. Spring precipitation, however, increased during initial growth stages when the plateau height was up to 40% of its present-day height, and then decreased with further plateau growth. During the Tibetan Plateau uplift, the difference between precipitation and evaporation was minimal during spring. When the plateau attained a height exceeding 60% of its present height, relatively low precipitation but high evaporation in spring led to a lower amount of ground moisture. In the case of the high plateau, sensible heat flux during summer and fall largely exceeded latent heat flux. Change was particularly significant for cases when the plateau reached 40–60% of its present-day height. The duration of the predominant sensible heat flux became longer with the uplift of the Tibetan Plateau. The period in which latent heat exceeded sensible heat seems to have been restricted to winter and early spring. The numeric experiments suggest that a significant drying of central Asia corresponded to the period in which the Tibetan Plateau exceeded approximately half its present-day height.