Uranyl adsorption and surface speciation at the imogolite-water interface: Self-consistent spectroscopic and surface complexation models

Macro- and molecular-scale knowledge of uranyl (U(VI)) partitioning reactions with soil/sediment mineral components is important in predicting U(VI) transport processes in the vadose zone and aquifers. In this study, U(VI) reactivity and surface speciation on a poorly crystalline aluminosilicate mineral, synthetic imogolite, were investigated using batch adsorption experiments, X-ray absorption spectroscopy (XAS), and surface complexation modeling. U(VI) uptake on imogolite surfaces was greatest at pH ∼7-8 (I = 0.1 M NaNO₃ solution, suspension density = 0.4 g/L [U(VI)]_i = 0.01-30 μM, equilibration with air). Uranyl uptake decreased with increasing sodium nitrate concentration in the range from 0.02 to 0.5 M. XAS analyses show that two U(VI) inner-sphere (bidentate mononuclear coordination on outer-wall aluminol groups) and one outer-sphere surface species are present on the imogolite surface, and the distribution of the surface species is pH dependent. At pH 8.8, bis-carbonato inner-sphere and tris-carbonato outer-sphere surface species are present. At pH 7, bis- and non-carbonato inner-sphere surface species co-exist, and the fraction of bis-carbonato species increases slightly with increasing I (0.1-0.5 M). At pH 5.3, U(VI) non-carbonato bidentate mononuclear surface species predominate (69%). A triple layer surface complexation model was developed with surface species that are consistent with the XAS analyses and macroscopic adsorption data. The proton stoichiometry of surface reactions was determined from both the pH dependence of U(VI) adsorption data in pH regions of surface species predominance and from bond-valence calculations. The bis-carbonato species required a distribution of surface charge between the surface and β charge planes in order to be consistent with both the spectroscopic and macroscopic adsorption data. This research indicates that U(VI)-carbonato ternary species on poorly crystalline aluminosilicate mineral surfaces may be important in controlling U(VI) mobility in low-temperature geochemical environments over a wide pH range (∼5-9), even at the partial pressure of carbon dioxide of ambient air (p_CO2 = 10^−3.45 atm).     

Impacts of regional warming on long‐term hypolimnetic anoxia and dissolved oxygen concentration in a deep lake

Although few reports have described long‐term continuous anoxia in aquatic systems, Lake Ikeda in Japan experienced such conditions in the hypolimnion from 1990 to 2010. The present study aimed to assess temporal fluctuations in the lake's thermal stability from 1978 to 2011 to understand the influence of regional climate change on hypolimnetic anoxia in this lake. Because complete vertical mixing, which supplies dissolved oxygen (DO) to the hypolimnion, potentially occurs on February, we calculated the Schmidt stability index (S) in February and compared it with hypolimnetic DO dynamics. Vertical water temperature profiles were calculated using a one‐dimensional model, and calculated temperatures and meteorological data were used to analyse annual fluctuations in water temperatures, thermocline depth, meteorological variables and S. We estimated that mean annual air and volume‐weighted water temperatures increased by 0.028 and 0.033 °C year^?1, respectively, from 1978 to 2011. Between 1986 and 1990, S and water temperature increased abruptly, probably due to a large upwards trend in air temperature (+0.239 °C year^?1). We hypothesize that a mixing regime that lacked overturn took effect at this time and that this regime lasted until 2011, when S was particularly small. These results demonstrate that abrupt climate warming in the late 1980s likely triggered the termination of complete mixing and caused the 21‐year period of successive anoxia in Lake Ikeda. We conclude that the lake response to a rapid shift in regional climate conditions was a key factor in changing the hypolimnetic water environment and that thermal stability in winter is a critical environmental factor controlling the mixing regime and anoxic conditions in deep lakes. Copyright © 2014 John Wiley & Sons, Ltd.     

A practical model to estimate photosynthetically active radiation using general meteorological elements in a temperate humid area and comparison among models

Although accurately evaluating photosynthetically active radiation is important, much effort is required to measure this radiation using a quantum sensor. We develop a new model that makes estimates using only general meteorological data—solar radiation, atmospheric pressure, air temperature, and relative humidity. Root mean square deviations for eight datasets at five sites in Japan were smaller than 5.2 %, similar to error in other studies and to individual differences of quantum sensors. Most root mean square deviations of nine previous models and our eight datasets are larger than that of the new estimation model, which performed well. This suggests that the model is useful for estimating photosynthetically active radiation in a temperate, humid area of Japan.     

加密自动气象站雨量计资料的质量控制 及其相关关系的研究

在长春—四平地区100 km×100 km的范围内,分布有平均间隔10 km左右的147个自动气象站。结合该区域雷达回波强度资料,对2007～2011年4～10月的气象站雨量计小时降水数据进行质量控制。多步骤质量控制结果显示,有141个自动站雨量计的数据通过了检查,删除了6个错误站点的数据,对有疑问时段的数据作了标记。 利用质量控制后的5年夏季半年自动站雨量计小时降水数据,进行相关关系统计分析表明：距离在10 km以内的雨量计测量,平均相关系数均能达到0.6以上;雨量计距离小于5 km,平均相关系数在0.7以上;而站点距离超过20 km,相关系数普遍降到0.4以下;随着统计时间的增长（从分钟到月降水量）,每个雨量计的测量值具有更高的空间代表性。     

Reconnaissance report on landslide disasters in northeast Japan following the M 9 T��hoku earthquake

An earthquake of M_w 9.0 struck the Pacific coast in northeast Japan on March 11, 2011 and was followed by a hugely damaging tsunami along 500 km of the Japanese coastline. An inland aftershock of M. 7.0 occurred on April 11; during which, surface fault ruptures appeared on land. A large variety of landslide disasters resulted from these earthquakes in various parts of northeastern Honshu, Japan. The full extent of the landslides is still being determined. This brief report introduces some of the landslide phenomena so far investigated by the Japanese Landslide Society. These are (1) failure of a water reservoir embankment dam in Sukagawa, Fukushima prefecture, (2) landslides and surface seismic fault rupture from the April 11 aftershock in Iwaki, Fukushima, (3) a concentration of surface failures at Matsushima Bay in Miyagi prefecture, and (4) small landslides on modified slopes in residential areas around Sendai city.     

Characteristics of neighborhood interaction in urban land-use changes: A comparative study between three metropolitan areas of Japan

Local spatial interaction between neighborhood land-use categories (i.e. neighborhood interaction) is an important factor which affects urban land-use change patterns. Therefore, it is a key component in cellular automata (CA)-based urban geosimulation models towards the simulation and forecast of urban land-use changes. Purpose of this paper is to interpret the similarities and differences of the characteristics of neighborhood interaction in urban land-use changes of different metropolitan areas in Japan for providing empirical materials to understand the mechanism of urban land-use changes and construct urban geosimulation models. Characteristics of neighborhood interaction in urban land-use changes of three metropolitan areas in Japan, i.e. Tokyo, Osaka, and Nagoya, were compared using such aids as the neighborhood interaction model and similarity measure function. As a result, urban land-use in the three metropolitan areas was found to have had similar structure and patterns during the study period. Characteristics of neighborhood interaction in urban land-use changes are quite different from land-use categories, meaning that the mechanism of urban land-use changes comparatively differs among land-use categories. Characteristics of neighborhood interaction reveal the effect of spatial autocorrelation in the spatial process of urban land-use changes in the three metropolitan areas, which correspond with the characteristics of agglomeration of urban land-use allocation in Japan. Neighborhood interaction amidst urban land-use changes between the three metropolitan areas generally showed similar characteristics. The regressed neighborhood interaction coefficients in the models may represent the general characteristics of neighborhood effect on urban land-use changes in the cities of Japan. The results provide very significant materials for exploring the mechanism of urban land-use changes and the construction of universal urban geosimulation models which may be applied to any city in Japan.     

The Inference of Geo-Mechanical Properties of Soft Rocks and their Degradation from Needle Penetration Tests

Needle penetration tests (NPTs) are used for inferring the uniaxial compressive strength of soft rocks, particularly in tunneling through squeezing rocks and foundations on weathered rocks in Japan. The device measures the applied load and the penetration depth of its needle. The ratio of applied load to penetration depth was originally called the needle penetration index (NPI). In this study, this device has been used to infer the geo-mechanical properties of soft rocks from Japan, Turkey, Indonesia, and Egypt. Various equations are presented to infer the geo-mechanical properties in terms of the NPI and compared with the experimental results. The possibility of evaluating the anisotropy of geo-mechanical properties is shown. Furthermore, the characterization of geo-mechanical properties of fault/fracture and slip (shear) surfaces is explained. Some additional equations are given to consider the degradation of geo-mechanical properties as a function of water content, weathering state, and number of cycles of freezing–thawing. Furthermore, the possibility of evaluating the time-dependency characteristics of soft rocks by needle penetration testing is discussed through experiments. It is shown that the effects of water content, weathering state, and number of cycles of freezing–thawing and time-dependency can be evaluated using the NPT technique.