The effect of iron on montmorillonite stability. (I) Background and thermodynamic considerations

It is envisaged that high-level nuclear waste (HLW) will be disposed of in underground repositories. Many proposed repository designs include steel waste canisters and bentonite backfill. Natural analogues and experimental data indicate that the montmorillonite component of the backfill could react with steel corrosion products to produce non-swelling Fe-rich phyllosilicates such as chamosite, berthierine, or Fe-rich smectite. In K-bearing systems, the alteration of montmorillonite to illite/glauconite could also be envisaged. If montmorillonite were altered to non-swelling minerals, the swelling capacity and self-healing properties of the bentonite backfill could be reduced, thereby diminishing backfill performance. The main aim of this paper was to investigate Fe-rich phyllosilicate mineral stability at the canister-backfill interface using thermodynamic modelling. Estimates of thermodynamic properties were made for Fe-rich clay minerals in order to construct approximate phase-relations for end-member/simplified mineral compositions in logarithmic activity space. Logarithmic activity diagrams (for the system Al₂O₃-FeO-Fe₂O₃-MgO-Na₂O-SiO₂-H₂O) suggest that if pore waters are supersaturated with respect to magnetite in HLW repositories, Fe(II)-rich saponite is the most likely montmorillonite alteration product (if f_O2(g) values are significantly lower than magnetite-hematite equilibrium). Therefore, the alteration of montmorillonite may not be detrimental to nuclear waste repositories that include Fe, as long as the swelling behaviour of the Fe-rich smectite produced is maintained. If f_O2(g) exceeds magnetite-hematite equilibrium, and solutions are saturated with respect to magnetite in HLW repositories, berthierine is likely to be more stable than smectite minerals. The alteration of montmorillonite to berthierine could be detrimental to the performance of HLW repositories.     

Water Self-Softening Processes at Waterfall Sites

Many rivers in tropical and subtropical karst regions are supersaturated with respect to CaCO3 and have high water hardness. After flowing through waterfall sites, river water is usually softened, accompanied by tufa formation, which is simply described as a result of water turbulence in fast-flowing water. In this paper, a series of laboratory experiments are designed to simulate the hydrological conditions at waterfall sites. The influences of air-water interface, water flow velocity, aeration and solid-water interface on water softening are compared and evaluated on a quantitative basis. The results show that the enhanced inorganic CO2 outgassing due to sudden hydrological changes occurring at waterfall sites is the principal cause of water softening at waterfall sites. Both air-water interface area and water flow velocity increase as a result of the "aeration effect", "low pressure effect" and "jet-flow effect" at waterfall sites, which greatly accelerates CO2 outgassing and therefore makes natural w     

Climatic change and Chinese population growth dynamics over the last millennium

The climate–population relationship has long been conceived. Although the topic has been repeatedly investigated, most of the related works are Eurocentric or qualitative. Consequently, the relationship between climate and population remains ambiguous. In this study, fine-grained temperature reconstructions and historical population data sets have been employed to statistically test a hypothesized relationship between temperature change and population growth (i.e., cooling associated with below average population growth) in China over the past millennium. The important results were: (1) Long-term temperature change significantly determined the population growth dynamics of China. However, spatial variation existed, whilst population growth in Central China was shown to be responsive to both long- and short-term temperature changes; in marginal areas, population growth was only sensitive to short-term temperature fluctuations. (2) Temporally, the temperature–population relationship was obscured in some periods, which was attributable to the factors of drought and social buffers. In summary, a temperature–population relationship was mediated by geographic factors, the aridity threshold, and social factors. Given the upcoming threat posed by climate change to human societies, this study seeks to improve our knowledge and understanding of the climate–society relationship.     

High-resolution climate simulation of the last glacial maximum

The climate of the last glacial maximum (LGM) is simulated with a high-resolution atmospheric general circulation model, the NCAR CCM3 at spectral truncation of T170, corresponding to a grid cell size of roughly 75 km. The purpose of the study is to assess whether there are significant benefits from the higher resolution simulation compared to the lower resolution simulation associated with the role of topography. The LGM simulations were forced with modified CLIMAP sea ice distribution and sea surface temperatures (SST) reduced by 1°C, ice sheet topography, reduced CO₂, and 21,000 BP orbital parameters. The high-resolution model captures modern climate reasonably well, in particular the distribution of heavy precipitation in the tropical Pacific. For the ice age case, surface temperature simulated by the high-resolution model agrees better with those of proxy estimates than does the low-resolution model. Despite the fact that tropical SSTs were only 2.1°C less than the control run, there are many lowland tropical land areas 4–6°C colder than present. Comparison of T170 model results with the best constrained proxy temperature estimates (noble gas concentrations in groundwater) now yield no significant differences between model and observations. There are also significant upland temperature changes in the best resolved tropical mountain belt (the Andes). We provisionally attribute this result in part as resulting from decreased lateral mixing between ocean and land in a model with more model grid cells. A longstanding model-data discrepancy therefore appears to be resolved without invoking any unusual model physics. The response of the Asian summer monsoon can also be more clearly linked to local geography in the high-resolution model than in the low-resolution model; this distinction should enable more confident validation of climate proxy data with the high-resolution model. Elsewhere, an inferred salinity increase in the subtropical North Atlantic may have significant implications for ocean circulation changes during the LGM. A large part of the Amazon and Congo Basins are simulated to be substantially drier in the ice age—consistent with many (but not all) paleo data. These results suggest that there are considerable benefits derived from high-resolution model regarding regional climate responses, and that observationalists can now compare their results with models that resolve geography at a resolution comparable to that which the proxy data represent.     

Fingerprinting of the Atlantic meridional overturning circulation in climate models to aid in the design of proxy investigations

It is desirable to design proxy investigations that target regions where properties reconstructed from calibrated parameters potentially carry high-fidelity information concerning changes in large-scale climate systems. Numerical climate models can play an important role in this task, producing simulations that can be analyzed to produce spatial “fingerprints” of the expected response of various properties under a variety of different scenarios. We will introduce a new method of fingerprinting the Atlantic meridional overturning circulation (AMOC) that not only provides information concerning the sensitivity of the response at a given location to changes in the large-scale system, but also quantifies the linearity, monotonicity and symmetry of the response. In this way, locations that show high sensitivities to changes in the AMOC, but that exhibit, for example, strongly nonlinear behavior can be avoided during proxy investigations. To demonstrate the proposed approach we will use the example of the response of seawater temperatures to changes in the strength of the AMOC. We present results from an earth-system climate model which has been perturbed with an idealized freshwater forcing scenario in order to reduce the strength of the AMOC in a systematic manner. The seawater temperature anomalies that result from the freshwater forcing are quantified in terms of their sensitivity to the AMOC strength in addition to the linearity and monotonicity of their response. A first-order reversal curve (FORC) approach is employed to investigate and quantify the irreversibility of the temperature response to a slowing and recovering AMOC. Thus, FORCs allow the identification of areas that are unsuitable for proxy reconstructions because their temperature versus AMOC relationship lacks symmetry.     

Characterization of dissolved organic matter across the Subtropical Convergence off the South Island,New Zealand

Dissolved organic matter (DOM) was investigated along a gradient across the Subtropical Convergence (STC) off the South Island, New Zealand. Ultrahigh resolution electrospray ionization Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR-MS), excitation emission matrix fluorescence (EEM) spectroscopy, and molecular lignin analysis techniques were used to study this DOM. The analysis revealed a group of compounds found only in the coastal DOM samples, which were also characterized by an elevated terrestrial DOM fluorescence pattern and elevated lignin content if compared to the offshore samples. This group exhibited a high degree of carbon unsaturation, as evident from high double bond equivalence minus oxygen values (DBE-O > 9) and maximum fluorescence intensity. Sulfur-containing molecular formulae for summer DOM samples were much more abundant across the entire transect of the STC compared to winter and exhibited distinctly different hydrogen:carbon and oxygen:carbon elemental ratios, suggesting a possible correlation between biological activity and sulfur compounds. The molecular formulae common to all STC samples were compared with those calculated for DOM extracted from freshwater collected from a stream discharging into Doubtful Sound (West Coast, New Zealand). ESI-FT-ICR-MS measurements undertaken in negative electrospray ionization (ESI?) mode indicated that 30% of the molecular formulae were present in both types of DOM, while in positive ESI mode (ESI+) over 90% of the formulae were present in all samples. Hence, a significant portion of the molecular formulae assigned to the solid-phase extractable DOM pool (SPE-DOM) appear to be identical in oceanic and freshwater samples.     

Predicting the dependency of a degree of saturation on void ratio and suction using effective stress principle for unsaturated soils

The paper presents an approach to predicting variation of a degree of saturation in unsaturated soils with void ratio and suction. The approach is based on the effective stress principle for unsaturated soils and several underlying assumptions. It focuses on the main drying and wetting processes and does not incorporate the effects of hydraulic hysteresis. It leads to the dependency of water retention curve (WRC) on void ratio, which does not require any material parameters apart from the parameters specifying WRC for the reference void ratio. Its validity is demonstrated by comparing predictions with the experimental data on four different soils taken over from the literature. Good correlation between the measured and predicted behaviour indirectly supports applicability of the effective stress principle for unsaturated soils. Copyright © 2009 John Wiley & Sons, Ltd.