Reference Materials in Geoanalytical Research -Review for 2004 and 2005

This review gives an overview of the use and development of reference materials of geochemical and environmental interest in the literature of the years 2004 and 2005. In these years the performance of existing methods has been improved and new geochemical applications using new techniques have been developed. Accordingly, there was an increasing need for new reference materials, especially for in situ microanalysis and for precise stable isotope measurements. In addition, there was a notable trend for further characterisation of existing reference materials, mainly for the platinum-group elements. This review focuses on five topics: reference materials for platinum-group elements, reference glasses for in situ microanalysis, zircon reference materials, isotopic reference materials, and the development and certification of reference materials.     

Structural Evolvement of Heating Treatment of Mg/AI-LDH and Preparation of Mineral Mesoporous Materials

Although hydrotalcite, or layered double hydroxides （LDHs）, is not a common mineral, it is an important material that can be easily synthesized in laboratory. In this study, structural evolvement and BET surface area changes of heat treated Mg/AI-LDH is evaluated by XRD, TEM and N2-BET analyses. The results indicate that the magnesium-aluminum LDH with carbonate as interlayer anion, periclase-like oxides was formed at temperatures of 400-800℃. Meanwhile, 2-3 nanometer mesoporous were formed during decomposition of LDH. However, the heat treated samples still preserve the morphology of the original LDH plates. Periclase-like formed from LDH heat treatment may re-hydrolyze and recover the structure of LDH. However, crystallinity of the recovered LDH is lower than that of the original LDH. This heat treatment will result in formation of （Mg, Al）-oxide nano-crystals and nanopores among the nano-crystals. When heating temperature exceeds 1000, the periclase-like （Mg, Al）-oxide is transformed into a composite with periclase （MgO） and spinel phases. The periclase can be re-hydrolyzed and dissolved in HCl solution. After acid treatment, the sample with a high surface area is composed of spinel nano-crystals and nanopores among them. Our results will provide a new and economic way to synthesize mesoporous materials through pathways of phase transformation of precursor materials with different composition.     

Modeling the cyclic swelling pressure of mudrock using artificial neural networks

The stochastic nature of the cyclic swelling behavior of mudrock and its dependence on a large number of interdependent parameters was modeled using Time Delay Neural Networks (TDNNs). This method has facilitated predicting cyclic swelling pressure with an acceptable level of accuracy where developing a general mathematical model is almost impossible. A number of total pressure cells between shotcrete and concrete walls of the powerhouse cavern at Masjed–Soleiman Hydroelectric Powerhouse Project, South of Iran, where mudrock outcrops, confirmed a cyclic swelling pressure on the lining since 1999. In several locations, small cracks are generated which has raised doubts about long term stability of the powerhouse structure. This necessitated a study for predicting future swelling pressure. Considering the complexity of the interdependent parameters in this problem, TDNNs proved to be a powerful tool. The results of this modeling are presented in this paper.     

Synchrotron IR study of hydrous ringwoodite (γ-Mg2SiO4) up to 30 GPa

High-pressure synchrotron infrared (IR) absorption spectra were collected between 650 and 4,000 cm⁻¹ at ambient temperature for hydrous Mg-ringwoodite (γ-Mg₂SiO₄) up to 30 GPa. The main feature in the OH⁻ stretching region is an extremely broad band centred at 3,150 cm⁻¹. The hydrogen bond is strong for most protons and the most probable site for protonation is the tetrahedral edge. With increasing pressure, this band shifts downward while decreasing its integrated intensity until disappearance at a pressure of 25 GPa. Only one band at 2,450 cm⁻¹ and an absorption plateau persist with a maximum wavenumber of 3,800 cm⁻¹. This behaviour is reversible upon pressure release. We interpret this as a second-order phase transition occurring in hydrated Mg-ringwoodite at high pressure (beyond ∼ 25 GPa). This result is compatible with the observation by Kleppe et al. (Phys Chem Miner 29:473–476, 2002a) who suggested the presence of Si–O–Si linkages and/or partial increase in the coordination of Si. Beyond the phase transition, the protons are delocalized and their environment on the ringwoodite structure is probably quite different from that at low pressure. Data obtained in situ at high pressures and temperatures are needed to better understand the effect of protonation on the structure and to better constrain this phase transition.     

Determining Q of near-surface materials from Rayleigh waves

High-frequency (≥2 Hz) Rayleigh wave phase velocities can be inverted to shear (S)-wave velocities for a layered earth model up to 30 m below the ground surface in many settings. Given S-wave velocity (V_S), compressional (P)-wave velocity (V_P), and Rayleigh wave phase velocities, it is feasible to solve for P-wave quality factor Q_P and S-wave quality factor Q_S in a layered earth model by inverting Rayleigh wave attenuation coefficients. Model results demonstrate the plausibility of inverting Q_S from Rayleigh wave attenuation coefficients. Contributions to the Rayleigh wave attenuation coefficients from Q_P cannot be ignored when Vs/V_P reaches 0.45, which is not uncommon in near-surface settings. It is possible to invert Q_P from Rayleigh wave attenuation coefficients in some geological setting, a concept that differs from the common perception that Rayleigh wave attenuation coefficients are always far less sensitive to Q_P than to Q_S. Sixty-channel surface wave data were acquired in an Arizona desert. For a 10-layer model with a thickness of over 20 m, the data were first inverted to obtain S-wave velocities by the multichannel analysis of surface waves (MASW) method and then quality factors were determined by inverting attenuation coefficients.     

地下管线探测工程的资料自动化整理

地下管线探测工程一般分为野外探测和室内资料整理两阶段。内业整理包括成果表的编制、管线综合分布平面图和管线数据库。由于管线探测工程数据多,为了充分利用外业探测成果,应用Visual Basic 6.0(VB6)开发了一套地下管线管理信息系统(UTMIS),该系统实现了地下管线探测工程内业整理的自动化,极大地提高了工作效率数据精确度。     

多孔结构矿物（岩石）及其环境修复材料的实用性

具有多孔结构的矿物(岩石)作为一类特殊的工业原材料，在环境修复领域的应用前景正在成为研究热点。本文从微孔的尺度、结构、形态、成分等表面固体特征出发，概括性地论述了凹凸棒石、海泡石、蒙脱石、沸石、硅藻土等十几种多孔结构矿物(岩石)在环境修复工程中用作过滤材料、吸附剂、离子交换剂和催化剂等材料时的基本特征和使用时应注意的问题。     

Laser Ablation ICP-MS Analysis of Geological Materials Prepared as Lithium Borate Glasses

A simple, rapid and precise method is described for determining trace elements by laser ablation (LA)-ICP-MS analysis in bulk geological materials that have been prepared as lithium borate glasses following standard procedures for XRF analysis. This approach reliably achieves complete sample digestion and provides for complementary XRF and LA-ICP-MS analysis of a full suite of major and trace elements from a single sample preparation. Highly precise analysis is enabled by rastering an ArF excimer laser (λ= 193nm) across fused samples to deliver a constant sample yield to the mass spectrometer without inter-element fractionation effects during each analysis. Capabilities of the method are demonstrated by determination of twenty five trace elements (Sc, Ti, V, Ga, Rb, Sr, Y, Zr, Nb, Cs, Ba, REE, Hf, Ta, Pb, Th and U) in a diverse range of geological reference materials that includes peridotites, basalts, granites, metamorphic rocks and sediments. More than 90% of determinations are indistinguishable from published reference values at the 95% confidence level. Systematic bias greater than 5% is observed for only a handful of elements (Zr, Nb and U) and may be attributed in part to inaccurate calibration values used for the NIST SRM 612 glass in the case of Zr and Nb. Detection limits for several elements, most notably La, are compromised at ultra-trace levels by impurities in the lithium borate flux but can be corrected for by subtracting appropriate procedural blanks. Reliable Pb analysis has proved problematic due to variable degrees of contamination introduced during sample polishing prior to analysis and from Pt-crucibles previously used to fuse Pb-rich samples. Scope exists for extending the method to include internal standard element/isotope spiking, particularly where integrated XRF analysis is not available to characterise major and trace elements in the fused lithium borate glasses prior to LA-ICP-MS analysis.     

A Reappraisal of Rb, Y, Zr, Pb and Th Values in Geochemical Reference Material BHVO-1

The geochemical reference material BHVO-1 was analysed by a variety of techniques over a six year period. These techniques included inductively coupled plasma-mass spectrometry and atomic emission spectroscopy (ICP-MS and ICP-AES, respectively), laser ablation ICP-MS and spark source mass spectroscopy. Inconsistencies between the published consensus values reported by Gladney and Roelandts (1988, Geostandards Newsletter) and the results of our study are noted for Rb, Y, Zr, Pb and Th. The values reported here for Rb, Y, Zr and Pb are generally lower, while Th is higher than the consensus value. This is not an analytical artefact unique to the University of Notre Dame ICP-MS facility, as most of the BHVO-1 analyses reported over the last ten to twenty years are in agreement with our results. We propose new consensus values for each of these elements as follows: Rb = 9.3 ± 0.2 μg g-1 (compared to 11 ± 2 μg g-1), Y = 24.4 ± 1.3 μg g-1 (compared to 27.6 ± 1.7 μg g-1), Zr = 172 ± 10 μg g-1 (compared to 179 ± 21 μg g-1), Pb = 2.2 ± 0.2 μg g-1 (compared to 2.6 ± 0.9 μg g-1) and Th = 1.22 ± 0.02 μg g-1 (compared to 1.08 ± 0.15 μg g-1).     

GIS中的应用模型及其管理研究

本文通过对ＧＩＳ模型库系统的研究，讨论了ＧＩＳ应用模型的管理及ＧＩＳ应用模型发展中的若干问题。