便携式Li-K分析仪的研制及其在锂辉石中锂的分析应用

我国锂钾主要矿产资源大多分布在西部偏远地区,其勘查找矿或综合利用迫切需要现场快速分析技术的支持。本文介绍了自行开发的便携式Li-K分析仪的主要性能及其在锂辉石中锂的分析应用。Li-K分析仪是一种基于大气压的液体阴极辉光放电光谱仪,以待测液体为放电阴极,实现了样品中Li、K等元素的原子化和激发。该仪器以光纤传导CCD光谱仪作为检测器,其波长范围为345~1015 nm,分辨率3 nm;以Li 670.78 nm和K 769.90 nm分析谱线,在仪器最佳工作条件下测定Li、K的精密度(RSD,n=14)均低于2%,检出限为0.03μg/m L,检测范围0.1~10μg/m L。研究表明,不同酸度和酸的类型对谱线强度影响较大,且存在显著的样品基体效应,标准曲线法分析锂辉石中Li的结果偏差高达267%;而标准加入法可克服基体效应的影响,获得与ICP-OES一致性较好的分析结果,为现场开展固体样品中Li的测定奠定了基础。     

Phase relation of CaSO<Subscript>4</Subscript> at high pressure and temperature up to 90 GPa and 2300 K

Calcium sulfate (CaSO₄), one of the major sulfate minerals in the Earth’s crust, is expected to play a major role in sulfur recycling into the deep mantle. Here, we investigated the crystal structure and phase relation of CaSO₄ up to ~90 GPa and 2300 K through a series of high-pressure experiments combined with in situ X-ray diffraction. CaSO₄ forms three thermodynamically stable polymorphs: anhydrite (stable below 3 GPa), monazite-type phase (stable between 3 and ~13 GPa) and barite-type phase (stable up to at least 93 GPa). Anhydrite to monazite-type phase transition is induced by pressure even at room temperature, while monazite- to barite-type transition requires heating at least to 1500 K at ~20 GPa. The barite-type phase cannot always be quenched from high temperature and is distorted to metastable AgMnO₄-type structure or another modified barite structure depending on pressure. We obtained the pressure–volume data and density of anhydrite, monazite- and barite-type phases and found that their densities are lower than those calculated from the PREM model in the studied P–T conditions. This suggests that CaSO₄ is gravitationally unstable in the mantle and fluid/melt phase into which sulfur dissolves and/or sulfate–sulfide speciation may play a major role in the sulfur recycling into the deep Earth.     

In situ high-temperature X-ray diffraction and spectroscopic study of fibroferrite,FeOH(SO<Subscript>4</Subscript>)·5H<Subscript>2</Subscript>O

The thermal dehydration process of fibroferrite, FeOH(SO₄)·5H₂O, a secondary iron-bearing hydrous sulfate, was investigated by in situ high-temperature synchrotron X-ray powder diffraction (HT-XRPD), in situ high-temperature Fourier transform infrared spectroscopy (HT-FTIR) and thermal analysis (TGA-DTA) combined with evolved gas mass spectrometry. The data analysis allowed the determination of the stability fields and the reaction paths for this mineral as well as characterization of its high-temperature products. Five main endothermic peaks are observed in the DTA curve collected from room T up to 800 °C. Mass spectrometry of gases evolved during thermogravimetric analysis confirms that the first four mass loss steps are due to water emission, while the fifth is due to a dehydroxylation process; the final step is due to the decomposition of the remaining sulfate ion. The temperature behavior of the different phases occurring during the heating process was analyzed, and the induced structural changes are discussed. In particular, the crystal structure of a new phase, FeOH(SO₄)·4H₂O, appearing at about 80 °C due to release of one interstitial H₂O molecule, was solved by ab initio real-space and reciprocal-space methods. This study contributes to further understanding of the dehydration mechanism and thermal stability of secondary sulfate minerals.     

Anisotropic mechanical properties of zircon and the effect of radiation damage

This study provides new insights into the relationship between radiation-dose-dependent structural damage due to natural U and Th impurities and the anisotropic mechanical properties (Poisson’s ratio, elastic modulus and hardness) of zircon. Natural zircon samples from Sri Lanka (see Muarakami et al. in Am Mineral 76:1510–1532, 1991) and synthetic samples, covering a dose range of zero up to 6.8 × 10¹⁸ α-decays/g, have been studied by nanoindentation. Measurements along the [100] crystallographic direction and calculations, based on elastic stiffness constants determined by Özkan (J Appl Phys 47:4772–4779, 1976), revealed a general radiation-induced decrease in stiffness (~54 %) and hardness (~48 %) and an increase in the Poisson’s ratio (~54 %) with increasing dose. Additional indentations on selected samples along the [001] allowed one to follow the amorphization process to the point that the mechanical properties are isotropic. This work shows that the radiation-dose-dependent changes of the mechanical properties of zircon can be directly correlated with the amorphous fraction as determined by previous investigations with local and global probes (Ríos et al. in J Phys Condens Matter 12:2401–2412, 2000a; Farnan and Salje in J Appl Phys 89:2084–2090, 2001; Zhang and Salje in J Phys Condens Matter 13:3057–3071, 2001). The excellent agreement, revealed by the different methods, indicates a large influence of structural and even local phenomena on the macroscopic mechanical properties. Therefore, this study indicates the importance of acquiring better knowledge about the mechanical long-term stability of radiation-damaged materials.     

The impact of boreal autumn SST anomalies over the South Pacific on boreal winter precipitation over East Asia

The possible mechanism behind the variability in the dipole pattern of boreal winter precipitation over East Asia is analyzed in this study. The results show that the SST anomalies(SSTAs) over the South Pacific Ocean(SPO) in boreal autumn are closely related to the variability in the dipole pattern of boreal winter precipitation over East Asia. The physical link between the boreal autumn SPO SSTAs and the boreal winter East Asian precipitation dipole pattern is shown to mainly be the seasonal persistence of the SPO SSTAs themselves. The seasonal persistence of the SPO SSTAs can memorize and transport the signal of the boreal autumn SSTAs to the following winter, and then stimulates a meridional teleconnection pattern from the SH to the NH, resulting in a meridional dipole pattern of atmospheric circulation over East Asia in boreal winter. As a major influencing factor, this dipole pattern of the atmospheric circulation can finally lead to the anomalous precipitation dipole pattern over East Asia in boreal winter. These observed physical processes are further confirmed in this study through numerical simulation. The evidence from this study, showing the impact of the SPO SSTAs in boreal autumn,not only deepens our understanding of the variability in East Asian boreal winter precipitation, but also provides a potentially useful predictor for precipitation in the region.     

Upper-Tropospheric Environment–Tropical Cyclone Interactions over the Western North Pacific: A Statistical Study

Based on 25-year(1987–2011) tropical cyclone(TC) best track data, a statistical study was carried out to investigate the basic features of upper-tropospheric TC–environment interactions over the western North Pacific. Interaction was defined as the absolute value of eddy momentum flux convergence(EFC) exceeding 10 m s~(-1)d~(-1). Based on this definition, it was found that 18% of all six-hourly TC samples experienced interaction. Extreme interaction cases showed that EFC can reach~120 m s~(-1)d~(-1) during the extratropical-cyclone(EC) stage, an order of magnitude larger than reported in previous studies.Composite analysis showed that positive interactions are characterized by a double-jet flow pattern, rather than the traditional trough pattern, because it is the jets that bring in large EFC from the upper-level environment to the TC center. The role of the outflow jet is also enhanced by relatively low inertial stability, as compared to the inflow jet. Among several environmental factors, it was found that extremely large EFC is usually accompanied by high inertial stability, low SST and strong vertical wind shear(VWS). Thus, the positive effect of EFC is cancelled by their negative effects. Only those samples during the EC stage, whose intensities were less dependent on VWS and the underlying SST, could survive in extremely large EFC environments, or even re-intensify. For classical TCs(not in the EC stage), it was found that environments with a moderate EFC value generally below ~25 m s~(-1)d~(-1) are more favorable for a TC's intensification than those with extremely large EFC.     

Preface to the Special Issue “Unified Perspective of Climate Variability and Change”

正Forty years ago,Klaus Wyrtki(1975)of University of Hawaii discovered that El Nino warming off South America is not a result of local wind change but a response to the relaxed equatorial trade winds some 10 000 km away near the international dateline.The Kelvin wave mechanism was quickly verified from wind-forced ocean model simulations.Consequent     

Competing impact of anthropogenic emissions and meteorology on the distribution of trace gases over Indian region

The spatial distribution of trace gases exhibit large spatial heterogeneity over the Indian region with an elevated pollution loading over densely populated Gangetic Plains (IGP). The contending role and importance of anthropogenic emissions and meteorology in deciding the trace gases level and distribution over Indian region, however, is poorly investigated. In this paper, we use an online regional chemistry transport model (WRF/Chem) to simulate the spatial distribution of trace gases over Indian region during one representative month of only three meteorological seasons namely winter, spring/summer and monsoon. The base simulation, using anthropogenic emissions from SEAC⁴RS inventory, is used to simulate the general meteorological conditions and the realistic spatial distribution of trace gases. A sensitivity simulation is conducted after removing the spatial heterogeneity in the anthropogenic emissions, i.e., with spatially uniform emissions to decouple the role of anthropogenic emissions and meteorology and their role in controlling the distribution of trace gases over India. The concentration levels of Ozone, CO, SO₂ and NO₂ were found to be lower over IGP when the emissions are uniform over India. A comparison of the base run with the sensitivity run highlights that meteorology plays a dominant role in controlling the spatial distribution of relatively longer-lived species like CO and secondary species like Ozone while short-lived species like NO_X and SO₂ are predominantly controlled by the spatial variability in anthropogenic emissions over the Indian region.