In situ time resolved synchrotron powder diffraction study of thaumasite

Structural changes during dehydration and subsequent decomposition in thaumasite Ca₃Si(SO₄)(CO₃)(OH)₆·12 H₂O were studied by in situ synchrotron powder diffraction between 303 and 1,098 K. Evolution of the crystal structure was observed through 28 structure refinements, by full profile Rietveld analysis performed in the P6₃ space group, between 300 and 417 K, whereupon the thaumasite structure was observed to breakdown. Within this temperature range, the cell parameters of thaumasite increased as a function of temperature in a nearly linear fashion up to about 393 K, at which temperature, a slight slope change was observed. Above 400 K, the thermogravimetric analysis revealed that the dehydration process proceeded very rapidly while the refined occupancy of water molecules dropped below a critical level, leading to instability in the thaumasite structure. At a same time, a remarkable change in the unit cell parameters occurring at about 417 K indicated that the crystal structure of thaumasite collapsed on losing the crystallization water and it turned amorphous. This result indicated that the dehydration/decomposition of thaumasite was induced by the departure of the crystallization water. At about 950 K, anhydrite and cristobalite crystallized from the thaumasite glass.     

利用场地观测计算地表通量

高原地表的感热和潜热通量在亚洲季风系统中有很重要的作用。由于高原地域辽阔，且自然环境较严酷，不利于建立完善的地面观测系统。因此，卫星遥感观测就成为测算高原整体感热和潜热通量的有效工具。地面场地的观测结果作为地表通量的真实值，对于卫星遥感测算是非常重要的。它也为构建陆面—大气模型提供了科学依据，是卫星资料的资料同化系统中的重要组成部分。 计算场地热量通量有几种不同的处理方法。最简单的方法利用有效的观测和试验的参数，可以给出稳定连续的估计。愈精确的Bowen比或者廓线的观测能给出愈精确的信息。综合了湍流测量及辐射测量、土壤热通量的观测结果的估计对陆面—大气相互作用进行了详细的描述，以适应模式的发展。从1998年开始，这些方法联合应用到青藏高原；场地通量观测方面的成果以及目前对其理解将在本文中做一概述。     

土体原位测试法在岩土工程中的应用

土体原位测试是工程勘察和检测的有效手段，通过统计其数据可以得出有效的经验公式，在工程中有一定的实用性。     

Kinetic study of the dehydroxylation of chrysotile asbestos with temperature by in situ XRPD

 The kinetics of the dehydroxylation of chrysotile was followed in situ at high temperature using real-time conventional and synchrotron powder diffraction (XRPD). This is the first time kinetics parameters have been calculated for the dehydroxylation of chrysotile. The value of the order of the reaction mechanism calculated using the Avrami model indicates that the rate-limiting step of the reaction is a one-dimensional diffusion with an instantaneous nucleation or a deceleratory rate of nucleation of the reaction product. Hence, the rate-limiting step is the one-dimensional diffusion of the water molecules formed in the interlayer region by direct condensation of two hydrogen atoms and an oxygen atom. The calculated apparent activation energy of the reaction in the temperature range 620–750 °C is 184 kJ mol⁻¹. The diffusion path is along the axis of the fibrils forming the fibers. The amorphous or short-range ordered dehydroxylate of chrysotile is extremely unstable because forsterite readily nucleates in the Mg-rich regions. Moreover, it is less stable than the dehydroxylate of kaolinite, the so-called metakaolinite, which forms mullite at about 950 °C. This difference is interpreted in terms of the different nature of the two ions Mg²⁺ and Al³⁺ and their function as glass modifier and glass-forming ion, respectively. Received: 10 April 2002 / Accepted: 7 January 2003 Acknowledgements This work is part of a COFIN project (04 Scienze della Terra, NR 17, 2000) supported by MURST. Dr Dapiaggi is kindly acknowledged for help during the data collection at the Dipartimento di Scienze della Terra, University of Milan.     

New Attempt to Reduce the Harm of Smoking: Reducing the Nitrosamines Level in Tobacco Smoke by Microwave Irradiation

In order to protect the environment and public health, microwave irradiation was investigated as a means of reducing the nitrosamines level of tobacco smoke under mild conditions where the microwave energy was 1 kW and the irradiation time was shorter than 2 min. The microwave‐induced elimination of nitrosamines such as N‐nitrosopyrrolidine (NPYR) and N‐nitrosodiphenylamine (NDPA) was investigated and the impact of the presence of water and salt in the medium on the reduction was assessed in detail. The existence of water in the medium was crucial for the microwave‐induced reduction of NDPA, because the rapid movement of water molecules under the influence of microwaves strongly affects the adjacent nitrosamines leading to their decomposition. This was the first time that microwaves have been used to directly irradiate cigarettes sealed in their packaging, and the nitrosamines content of tobacco and smoke of these irradiated cigarettes were analyzed with care. Irradiation for 90 s with microwave energy of 1kW was seen to reduce 25 to 30% of the nitrosamines in tobacco and 50 to 60% of the levels present in the mainstream smoke of the cigarette. Moreover, lower mutagenic activity and higher CHO cell livability were found for the irradiated cigarettes in comparison with the control according to the results of in vitro tests.     

In situ measurements of contributions to the global electrical circuit by a thunderstorm in southeastern Brazil

The global electrical circuit, which maintains a potential of about 280 kV between the earth and the ionosphere, is thought to be driven mainly by thunderstorms and lightning. However, very few in situ measurements of electrical current above thunderstorms have been successfully obtained. In this paper, we present dc to very low frequency electric fields and atmospheric conductivity measured in the stratosphere (30–35 km altitude) above an active thunderstorm in southeastern Brazil. From these measurements, we estimate the mean quasi-static conduction current during the storm period to be 2.5 ± 1.25 A. Additionally, we examine the transient conduction currents following a large positive cloud-to-ground (+ CG) lightning flash and typical − CG flashes. We find that the majority of the total current is attributed to the quasi-static thundercloud charge, rather than lightning, which supports the classical Wilson model for the global electrical circuit.     

中国东北南部地区冬季气温异常的海气背景分析

利用1951—2005年中国沈阳、通化、营口、丹东气温和北半球500 hPa高度及北太平洋海温资料,分析了中国东北南部地区冬季气温的异常变化及其海气背景。结果表明:中国东北南部地区冬季气温具有明显的年代际变化特征;冬季异常冷暖年份,其同期与前期500 hPa高度和海温距平场分布具有明显不同;前期春季(3—5月)贝加尔湖高压和西太平洋副热带高压的强弱变化,西风漂流区海温、赤道东太平洋关键区海温及2个海区海温距平差,对中国东北南部地区冬季气温的异常变化均具有较好的预测指示意义。前期夏季(7—9月)赤道东太平洋关键区海温对中国东北南部地区冬季气温异常变化具有指示性。     

Identification of the Hualien soil-structure interaction system

This article demonstrates how system identification techniques can be successfully applied to a soil-structure interaction system in conjunction with the results of the forced vibration tests on the Hualien large-scale seismic test structure which was recently built in Taiwan for an international joint research. The parameters identified are the shear moduli of several near-field soil regions as well as Young's moduli of the shell sections of the structure. The soil-structure interaction system is represented by the finite element method combined with infinite element formulation for the unbounded layered soil medium. Preliminary investigations are carried out on the results of the static stress analysis for the soil medium and the results of the in-situ tests to divide the soil-structure system into several regions with homogeneous properties and to determine the lower and upper bounds of the parameters for the purpose of identification. Then two sets of parameters are identified for two principal directions based on the forced vibration test data by minimizing the estimation error using the constrained steepest descent method. The simulated responses for the forced vibration tests using the identified parameters show excellent agreement with the test data. The present estimated parameters are also found to be well compared with the average value of those by other researchers in the joint project.     

Continuous Multi‐probe Measurements in Fastflowing Waters Using a Hydrographic Slot

Taking continuous spatiotemporal in situ measurements with multi‐probes in fast‐flowing waters/rivers can be problematic because the sensors may be damaged by high shear forces and flotsam. To protect the multi‐probe and to enable easy access for the maintenance and calibration of the sensors, a special multi‐probe holder fixed in a hydrographic slot was developed. The validation of the probe system revealed a “memory effect” at short time scales (< 10 s) within sharp gradients caused by the overflow container of the multi‐probe rack keeping the sensors submerged in the sample water. Continuously recorded data (conductivity, temperature, pH, oxygen concentration and saturation, as well as in vivo fluorescence of chlorophyll‐a) from a research cruise on board the RV ALBIS along the river Elbe (river km 309) and entering the river Saale are presented. This river stretch upstream of the city of Magdeburg to the mouth of the Saale tributary was found to have a complex physicochemical character, which is attributable to the long mixing process of water from the river Saale and the river Elbe.     

Solubility of FeO in (Mg,Fe)SiO3 perovskite and the post-perovskite phase transition

Phase relations in Mg_0.5Fe_0.5SiO₃ and Mg_0.25Fe_0.75SiO₃ were investigated in a pressure range from 72 to 123 GPa on the basis of synchrotron X-ray diffraction measurements in situ at high-pressure and -temperature in a laser-heated diamond-anvil cell (LHDAC). Results demonstrate that Mg_0.5Fe_0.5SiO₃ perovskite is formed as a single phase at 85–108 GPa and 1800–2330 K, indicating a high solubility of FeO in (Mg,Fe)SiO₃ perovskite at high pressures. Post-perovskite appears coexisting with perovskite in Mg_0.5Fe_0.5SiO₃ above 106 GPa at 1410 K, the condition very close to the post-perovskite phase transition boundary in pure MgSiO₃. The coexistence of perovskite and post-perovskite was observed to 123 GPa. In addition, post-perovskite was formed coexisting with perovskite also in Mg_0.25Fe_0.75SiO₃ bulk composition at 106–123 GPa. In contrast to earlier experimental and theoretical studies, these results show that incorporation of FeO stabilizes perovskite at higher pressures. This could be due to a larger ionic radius of Fe²⁺ ion, which is incompatible with a small Mg²⁺ site in the post-perovskite phase.