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).     

Geoid determination using adapted reference field, seismic Moho depths and variable density contrast

 The traditional remove-restore technique for geoid computation suffers from two main drawbacks. The first is the assumption of an isostatic hypothesis to compute the compensation masses. The second is the double consideration of the effect of the topographic–isostatic masses within the data window through removing the reference field and the terrain reduction process. To overcome the first disadvantage, the seismic Moho depths, representing, more or less, the actual compensating masses, have been used with variable density anomalies computed by employing the topographic–isostatic mass balance principle. In order to avoid the double consideration of the effect of the topographic–isostatic masses within the data window, the effect of these masses for the used fixed data window, in terms of potential coefficients, has been subtracted from the reference field, yielding an adapted reference field. This adapted reference field has been used for the remove–restore technique. The necessary harmonic analysis of the topographic–isostatic potential using seismic Moho depths with variable density anomalies is given. A wide comparison among geoids computed by the adapted reference field with both the Airy–Heiskanen isostatic model and seismic Moho depths with variable density anomaly and a geoid computed by the traditional remove–restore technique is made. The results show that using seismic Moho depths with variable density anomaly along with the adapted reference field gives the best relative geoid accuracy compared to the GPS/levelling geoid. Received: 3 October 2001 / Accepted: 20 September 2002 Correspondence to: H.A. Abd-Elmotaal     

国家地理空间信息基准框架工程建设

提出了国家地理空间信息基准框架内改进与更新原有的大地坐标基准、高程基准和重力基准的建设道路及解决原则。     

高斯平面坐标换算到测区平均高程面上的方法

依据高斯投影原理，提出了一种在高斯平面与任决高程平面间进行坐标转换的方法，并设计了相应的计算软件。     

氯对测定化合水的影响及其校正研究

用差热和热（失）重法、ｐＨ值检验、离子色谱等分析方法考察和证实了Ｃｌ－对平菲尔特管重量法测定化合水（Ｈ２Ｏ＋）的干扰，研究其影响规律，提出用系数校正方法可获得Ｈ２Ｏ＋的准确结果。方法用于含氯深海沉积物和大洋多金属结核标准物质中Ｈ２Ｏ＋的定值分析，取得满意结果     

多金属结核中二氧化锰的测定

用过量的含有Ｈ２ＳＯ４的（ＮＨ４）２Ｆｅ（ＳＯ４）２溶液分解多金属结核的同时，还原了试样中的ＭｎＯ２，然后以Ｋ２Ｃｒ２Ｏ７标准溶液滴定测定了多金属结核中的ＭｎＯ２。就样品分解过程中的加热温度和时间对测定结果的影响及标准溶液的标定等问题进行了讨论，经多次测定，方法重现性好。应用此方法为新研制的多金属结核标准物质提供了ＭｎＯ２的定值数据，其结果与初定值相符，无剔除值，精密度（ＲＳＤ，ｎ＝８）小于０６％。     

深基础护坡桩的设计与施工中的几个问题

着重介绍了间隔式钻孔灌注桩在挡土护坡技术中的应用方法，设计时的主要参考依据，计算土压力理论的应用原则以及施工中需注意的几个问题，为进行深基础挡土护坡的工程提供了部分参考依据。     

A Reflection on Mg, Cd, Ca, Li and Si Isotopic Measurements and Related Reference Materials

This contribution aims to report the reflections we had with the scientific community during two international workshops on reference materials for stable isotopes in Davos (2002) and Nice (2003). After evaluating the isotopic homogeneity of some existing reference materials, based on either certificates, literature data or specific inter-laboratory rounds, we confirm these as primary reference materials or propose new ones relative to which stable isotope compositions should be reported. We propose DSM-3 for Mg, NIST SRM 915a for Ca, L-SVEC for Li and NBS28 for Si. Cadmium does not yet have a well identified delta zero material, although three commercial mono-elemental Cd solutions have yielded the same isotopic composition relative to one another. In order to scale the linearity of any mass spectrometer, some secondary reference materials are also proposed: Cambridge-1 solution for Mg, the "Münster-Cd" and JEPPIM Cd solutions for Cd and the "Big Batch" silicate for Si. The team from Nancy propose to prepare a mixed spike solution for Li isotopes. Well-characterised natural samples such as ocean or continental waters, diatoms, sponges, rocks and minerals are needed to validate the entire analytical procedure, particularly to take into account the effect of sample mineralisation and of chemical manipulations for elemental separation prior to analysis.     

Precise/ Small Sample Size Determinations of Lithium Isotopic Compositions of Geological Reference Materials and Modern Seawater by MC-ICP-MS

The Li isotope ratios of four international rock reference materials, USGS BHVO-2, GSJ JB-2, JG-2, JA-1 and modern seawater (Mediterranean, Pacific and North Atlantic) were determined using multi-collector inductively coupled plasma-mass spectrometry (MC-ICP-MS). These reference materials of natural samples were chosen to span a considerable range in Li isotope ratios and cover several different matrices in order to provide a useful benchmark for future studies. Our new analytical technique achieves significantly higher precision and reproducibility (< ± O.3%o 2s) than previous methods, with the additional advantage of requiring very low sample masses of ca . 2 ng of Li.