海南岛第四纪玄武岩风化壳中次生矿物转变与时间的关系

本文采用X射线分析法,从分析风化壳中的次生矿物入手,研究了海南岛北部不同地质年龄的第四纪玄武岩风化壳中次生矿物增长数量与风化时间的关系。两者关系的回归方程为Y=4.1898 207.30t,其中Y为次生矿物的含量(g/cm~2),t为风化时间(Ma)。相关系数γ=0.9977。每0.01Ma次生矿物平均增长2.2164g/cm~2。     

Precise and Accurate Doping of Nanoporous Silica Gel for the Synthesis of Trace Element Microanalytical Reference Materials

This study presents an experimental procedure to fabricate high‐purity silica glass containing a selected element at a specified mass fraction. The procedure was used to prepare glasses doped with trace‐level mass fractions of Ti with the goal of improving analytical confidence when measuring trace elements in quartz. Systematic tests were performed to determine the ideal conditions and procedures for doping nanoporous silica gel with the highest efficiency of dopant recovery. Silica gel was cleaned in concentrated HCl, immersed in a non‐polar doping medium at a controlled pH and doped with precise quantities of ICP‐MS standard solution. Using liquids composed of longer chain molecules as the doping medium diminishes recovery, suggesting that large molecules could obstruct nanopores to inhibit capillary uptake of the dopant. A control experiment using crystalline quartz reinforced the effectiveness of nanoporous silica gel for doping with trace‐level precision. Layered aggregates of silica gel doped with different Ti mass fractions were hot‐pressed to create multi‐layered reference materials that were analysed with multiple techniques at a variety of spatial scales. Analyses at the intra‐grain scale (cathodoluminescence scanning electron microscopy, electron probe microanalysis), at the single grain scale (SIMS), at the sample layer scale (EPMA, laser ablation‐ICP‐MS) and at the bulk scale (ICP‐OES) demonstrated acceptable homogeneity at sample volumes characteristic of most microanalysis techniques and show that nanoporous silica gel holds promise as a highly retentive doping substrate for preparing reference materials for laser‐, electron‐ and ion‐beam microanalysis.     

MINERALOGY OF COASTAL DEPOSITS OF NORTH-WESTERN SEA OF JAPAN

Distribution of heavy, light and clay minerals in Late Pleistocene—Holocene deposits from different coastal environments (beaches, lagoons, dunes, relict lakes, ria bays and inlets, open inlets) was analysed. It was established that mineralogical composition of coastal deposits was a result of provenance and its hypergenous changes, transformation of material within transit zone, and accumulative conditions of inshore zone. Contents of stable minerals increase in deposits of the inlets confined to mouths of the small streams and in horizons of the sections, formed during regressive phases. Unstable minerals amount is higher in deposits of inlets, confined to mouths of the large river. The clay mineral fraction of shelf sediments consists mostly of illite. Authigenous pyrites dominate in deposits of ria bays, lagoons and relict lakes, formed during transgressive phases. Volcanic glass, found in deposits, is product of Holocene eruptions of Baegdusan (Baitushen) Volcano.     

Quantification of Water Content and Speciation in Synthetic Rhyolitic Glasses: Optimising the Analytical Method of Confocal Raman Spectrometry

Quantification of water content in silicate glasses is of vital significance in understanding magma evolution and metamorphic anataxis. Here we provide a method for the determination of total dissolved water content and water speciation in silicate melts by confocal laser Raman spectrometry based on a set of hydrous rhyolitic glasses. A series of alumino-silicate glasses with water contents from 0.33 to 9.05% m/m were synthesised in a piston cylinder apparatus. Synchrotron-FTIR mapping shows that these glasses have relatively homogeneous distributions of dissolved water. Total water contents of the glasses were precisely measured by TC/EA-MS and FTIR. Both external and internal calibration were established for the quantitative analysis of water content and water speciation in the silicate glasses based on excellent linear correlation between total dissolved water content and integrated area of the water Raman band. Furthermore, by decomposing the total water Raman bands into four Gaussians components, the relative concentration of water speciation (OH groups and molecules H₂O_m) dissolved in the glasses was determined with a similar trend to water speciation data derived from FTIR. We suggest that the relative concentration of water speciation can be estimated in rhyolitic glasses with 4–8% m/m H₂O. Our work provides an accurate method to determine total water content and a potential tool to limit the relative concentration of water speciation dissolved in silicic glasses.     

Highly alkaline,high-temperature hydrothermal fluids in the early Archean ocean

Based on the petrology of hydrothermally altered Archean basaltic greenstones, thermodynamic calculations of phase equilibria were conducted to estimate the composition of a high-temperature (∼350 °C) hydrothermal fluid in an Archean subseafloor basalt-hosted hydrothermal system. The results indicate that the hydrothermal fluid was highly alkaline attributed to the presence of calcite in the alteration minerals under a high-CO₂ condition, and predict a generation of SiO₂-rich, Fe-poor hydrothermal fluids in the Archean subseafloor hydrothermal system. The chemically reactive mixing zones between alkaline hydrothermal fluids and slightly acidic-neutral seawater are characterized by inverse pH and chemical polarity to modern hydrothermal systems, leading to extensive precipitation of silica and iron oxyhydroxides on/under the seafloor. Such processes can be responsible for the abiotic formation of voluminous chert and subseafloor silica dike, the mechanism of silicification, and the pH-controlled generation of banded iron formation that has been arising mainly from the redox chemistry in the Archean ocean. Such high-temperature alkaline fluids could have had a significant role not only in the early ocean geochemical processes but also in the early evolution of life.     

Electron Probe Microanalysis of Environmental Samples: Preparation of Reference Materials, Correction for Particle Size Effects and Representative Results on Sediments Recovered from Snow, Power Station Fly Ash and Bone Samples

In this paper we report the results of electron probe X-ray microanalysis (EPMA) that was used to study environmental materials. The mode of preparation and certification of reference samples based on a basaltic glass matrix for environmental applications of EPMA is described. These samples were prepared containing scandium, strontium and barium (from 0.03 up to 7% m/m) and an evaluation was made of homogeneity, their stability to local heating, followed by analysis by independent methods for certification of composition. Matrix correction procedures for the EPMA technique have been developed for particles having a size commensurable with the volume of X-ray generation. An analytical equation for the size factor is proposed and two techniques for selecting optimum conditions for the analysis of environmental samples by EPMA are reported. These procedures provided satisfactory results when utilized in analysing sediments recovered from snow, coal fly ash and the bones of animals and fish, results from which can be used as indicators for evaluating the pollution level of the lower atmosphere, surface and ground water, as well as revealing pollution mechanisms.     

Nitrate pollution of ground waters from shallow basaltic aquifers,Deccan Trap Hydrologic Province,India

Analyses of groundwater samples collected from several locations in a small watershed of the Deccan Trap Hydrologic Province, indicated anomalously higher values of nitrate than the background. However, the NO₃ concentrations in water from dug wells under pastureland where the subsurface material consisted of stony waste were minimum. The maximum values were reported for water from dug wells where the principal land use was agricultural. Lowering of NO₃ values under shallow water-table conditions suggests denitrification. Higher concentrations of nitrate determined for samples collected from the wells with a deeper water-table indicate that denitrification process is inactive. The high values of nitrate coinciding with agricultural land use indicate fertilizers as the main source of nitrate pollution of ground-water. Decrease in Cl/NO₃ ratio for agricultural land use confirms this inference.     

Thermodynamic properties,low-temperature heat-capacity anomalies,and single-crystal X-ray refinement of hydronium jarosite, (H<Subscript>3</Subscript>O)Fe<Subscript>3</Subscript>(SO<Subscript>4</Subscript>)<Subscript>2</Subscript>(OH)<Subscript>6</Subscript>

Crystals of hydronium jarosite were synthesized by hydrothermal treatment of Fe(III)–SO₄ solutions. Single-crystal XRD refinement with R₁=0.0232 for the unique observed reflections (|F_o| > 4_F) and wR₂=0.0451 for all data gave a=7.3559(8) Å, c=17.019(3) Å, V^o=160.11(4) cm³, and fractional positions for all atoms except the H in the H₃O groups. The chemical composition of this sample is described by the formula (H₃O)_0.91Fe_2.91(SO₄)₂[(OH)_5.64(H₂O)_0.18]. The enthalpy of formation (H^o_f) is –3694.5 ± 4.6 kJ mol^–1, calculated from acid (5.0 N HCl) solution calorimetry data for hydronium jarosite, -FeOOH, MgO, H₂O, and -MgSO₄. The entropy at standard temperature and pressure (S^o) is 438.9±0.7 J mol^–1 K^–1, calculated from adiabatic and semi-adiabatic calorimetry data. The heat capacity (C_p) data between 273 and 400 K were fitted to a Maier-Kelley polynomial C_p(T in K)=280.6 + 0.6149T–3199700T^–2. The Gibbs free energy of formation is –3162.2 ± 4.6 kJ mol^–1. Speciation and activity calculations for Fe(III)–SO₄ solutions show that these new thermodynamic data reproduce the results of solubility experiments with hydronium jarosite. A spin-glass freezing transition was manifested as a broad anomaly in the C_p data, and as a broad maximum in the zero-field-cooled magnetic susceptibility data at 16.5 K. Another anomaly in C_p, below 0.7 K, has been tentatively attributed to spin cluster tunneling. A set of thermodynamic values for an ideal composition end member (H₃O)Fe₃(SO₄)₂(OH)₆ was estimated: G^o_f= –3226.4 ± 4.6 kJ mol^–1, H^o_f=–3770.2 ± 4.6 kJ mol^–1, S^o=448.2 ± 0.7 J mol^–1 K^–1, C_p (T in K)=287.2 + 0.6281T–3286000T^–2 (between 273 and 400 K).     

Preliminary Study on the Effect of Water Glass Impregnation on the Rock-Magnetic Properties of Baked Clay

A common practice in archaeomagnetic studies in many laboratories is the impregnation of the material with water glass (siliceous gel) in order to achieve better consolidation before cutting. The purpose of this study is to establish if and how the presence of water glass in the burnt clay material affects its magnetic properties during heating. We describe experiments designed to monitor the alterations in isothermal remanence and magnetic susceptibility for two sets of specimens - non-impregnated and impregnated with water glass. Our results show that water glass can cause considerable changes in magnetic susceptibility, but the remanent magnetization is not influenced significantly.