催化分光光度新方法测定痕量钌

研究了在HAc-NaAc介质中,α,α′-联吡啶存在下,Ru(Ⅲ)催化KBrO_3氧化溴甲酚绿褪色反应及其动力学条件,建立了一个测定痕量Ru(Ⅲ)的高灵敏度新方法。方法的检出限为2.0×10~(-10)g/ml Ru,测定范围为0～8ng/ml。     

碘的分析现状

综述了碘(主要是痕量碘)的分析概况及进展,包括测定方法(分光光度法、容量法、离子色谱、电分析化学方法、中子活化分析法、原子吸收光谱、发射光谱、质谱、X荧光光谱及测温法)及分离富集方法,还介绍了流动注射分析技术在测碘中的应用。     

化探样品中微量铅、锡、铬、钼和钴的发射光谱法同时测定

本文以CdCl_2·2.5H_2O为反应剂,采用“下垫上滴”缓冲刺的装样形式,通过大量镉盐的蒸发控制电极温度,使被测元素预先分馏,有效地改善了它们的蒸发行为,同时,减小了基体效应、光谱背景。本法其有良好的精密度和准确度,各元素的检出限(×10~(-5))分别为:Pb(1),Sn(0.37),Cr(1.8),Ni(3.51,Mo(0.1)和Co(0.38),其相对标准偏差(RSD)为±3.7—9.5%     

Determination of focal coordinates of near earthquakes in an area of unknown crustal parameters

Summary A new computation method is described which determines the focal coordinates, theP _n-andP _G-velocity, the focal time and the Moho-depth in the case of near earthquakes. The method is provided especially for areas where the crustal parameters are insufficiently known. It presumes that the standard error ofP _n-andP _G-arrival times is a minimum. The problem turns out to represent the solution of a set of at least seven equations with seven unknown parameters. Four of these unknowns can be separated in advance. This leads to a considerable simplification. The three remaining unknowns are the focal coordinates. Their best fitting values are found by the gradient method. An example is presented which shows how errors can arise if the initial trial coordinate is chosen at an unfavourable position.     

A comparison of methods for the inversion of airborne gravity data

Four integral-based methods for the inversion of gravity disturbances, derived from airborne gravity measurements, into the disturbing potential on the Bjerhammar sphere and the Earths surface are investigated and compared with least-squares (LS) collocation. The performance of the methods is numerically investigated using noise-free and noisy observations, which have been generated using a synthetic gravity field model. It is found that advanced interpolation of gravity disturbances at the nodes of higher-order numerical integration formulas significantly improves the performance of the integral-based methods. This is preferable to the commonly used one-point composed Newton–Cotes integration formulas, which intrinsically imply a piecewise constant interpolation over a patch centered at the observation point. It is shown that the investigated methods behave similarly for noise-free observations, but differently for noisy observations. The best results in terms of root-mean-square (RMS) height-anomaly errors are obtained when the gravity disturbances are first downward continued (inverse Poisson integral) and then transformed into potential values (Hotine integral). The latter has a strong smoothing effect, which damps high-frequency errors inherent in the downward-continued gravity disturbances. An integral method based on the single-layer representation of the disturbing potential shows a similar performance. This representation has the advantage that it can be used directly on surfaces with non-spherical geometry, whereas classical integral-based methods require an additional step if gravity field functionals have to be computed on non-spherical geometries. It is shown that defining the single-layer density on the Bjerhammar sphere gives results with the same quality as obtained when using the Earths topography as support for the single-layer density. A comparison of the four integral-based methods with LS collocation shows that the latter method performs slightly better in terms of RMS height-anomaly errors.     

Platinum-Group Element and Rhenium Concentrations in Low Abundance Reference Materials

One or two gram aliquots of twelve reference materials with low platinum-group element (PGE) abundances (Ir concentrations ranging from 30 to 510 pg g^-1) were analysed by isotope dilution ICP-MS using an on-line chromatographic matrix separation after acid digestion in a high pressure asher (HPA-S) to determine the concentrations of Ru, Pd, Re, Ir and Pt. Osmium concentrations were determined via ID-ICP-MS but as volatile OsO₄, whereas Rh concentrations were calculated by comparing the peak areas of the chromatographic peak with that of a standard solution. Validation of the method was performed and the concepts of traceability and measurement uncertainty were applied to assure comparability. The reference materials BCR-2, BHVO-1, BHVO-2, BIR-1, DNC-1, EN026 10D-3, MAG-1, RGM-1, SCo-1, SDO-1, TDB-1 and W-2 were investigated to test for their usefulness for certification. The use of TDB-1 is highly recommended because it is homogeneous at the two gram level and many values based on several different analytical procedures have been published. It is recommended that our efforts should focus on the certification of this reference material to reduce the uncertainties of its currently certified values (Pd and Pt only) and to assign certified values to the other PGE and Re. It is necessary to have at least one well-characterised RM for validation of methods applied to the analysis of PGE and Re in low abundance samples, although the matrix of TDB-1 might not completely match those of many samples.     

Pressurised Extraction Using Dilute Ammonia: A Simple Method for Determination of Iodine in Soil, Sediment and Biological Samples by Inductively Coupled Plasma-Mass Spectrometry

A simple sample treatment method for the accurate and precise determination of iodine in soil, sediment and biological samples by inductively coupled plasma-mass spectrometry (ICP-MS) is described. Iodine in samples was extracted in screw top PTFE-lined stainless steel bombs using a 10% v/v ammonia solution at 185 C for 18 hours (overnight), after which the extract was introduced into the ICP-MS for direct measurement. ¹²⁶Te was employed as the internal standard to compensate for matrix effects and instrument drift. The limit of detection (LOD, three times the standard deviation of the procedural blank solution, expressed as the concentration in the sample solution) was 0.003 ng ml-^-1. The limit of quantitation (LOQ, ten times the standard deviation of the procedural blank solution, expressed as the concentration in the solid samples, dilution factor DF = 100) was 0.01 μg g-^-1 (dry mass). The accuracy and precision of the method were demonstrated by analysing different Chinese geological certified reference materials (soils, stream sediments and a hair sample). The measured concentrations were in a good agreement with the certified values indicating that bias in the method was not significant. The precision (n = 10) for different concentrations ranged from 1.82% to 4.32% RSD. Comparison of the ammonia extraction procedure with a "sintering" method indicated that there was no significant difference in results obtained with the two methods for geological soil and stream sediment samples. However, for biological samples, such as hair, kelp, tea etc., the results obtained by the sintering method were far below those of the ammonia extraction method. The ammonia extraction has advantages, as it is simpler than the "sintering" method, and has a lower procedural blank, better detection limits and reproducibility. Due to the simplicity of the method, a high rate of sample throughput is possible.     

双星姿态测量的算法及双值问题

给出了双星姿态测量的两种算法，并从几何和代数两个方面证实其存在双值问题；探讨了双值问题与精度衰减因子(DOP)之间的关系，并提出了双值问题的解决方案。     

辽河断陷古潜山古生界的厘定及其地质意义

辽河断陷以碳酸盐岩和砂页岩为主的古潜山地层一直全部划归中、新元古界。由于在该套地层的部分岩石薄片中发现交代残余的动物化石碎片，因此提出辽河断陷有古生界存在的新观点。通过牙形石、微古植物、动物化石和岩性组合的研究，对这套地层进行了重新厘定，建立了古生代寒武纪、奥陶纪、石炭纪和二叠纪地层层序。研究成果表明，辽河断陷存在古生界储层，古生代潜山并非单斜．而是由被断裂改造的褶皱组成的断块。这一成果为重新认识潜山的内幕构造特征和油气储层分布规律奠定了基础。     

Multi-Element Isotope Dilution Sector Field ICP-MS: A Precise Technique for the Analysis of Geological Materials and its Application to Geological Reference Materials

We present a multi-element technique for the simultaneous determination of twelve trace elements in geological materials by combined isotope dilution (ID) sector field inductively coupled plasma-mass spectrometry (SF-ICP-MS) following simple sample digestion. In addition, the concentrations of fourteen other trace elements have been obtained using the ID determined elements as internal standards. This method combines the advantages of ID (high precision and accuracy) with those of SF-ICP-MS (multi-element capability, fast sample processing without element separation) and overcomes the most prevailing drawbacks of ICP-MS (matrix effects and drift in sensitivity). Trace element concentration data for BHVO-1 (n = 5) reproduced to within 1–3% RSD with an accuracy of 1–2% relative to respective literature values for ID values and 2–3% for all other values. We have applied this technique to the analysis of seventeen geological reference materials from the USGS, GSJ and IAG. The sample set also included the new USGS reference glasses BCR-2G, BHVO-2G and BIR-1G, as well as the MPI-DING reference glasses KL2-G and ML3B-G, and NIST SRM 612. Most data agreed within 3–4% with respective literature data. The concentration data for the USGS reference glasses agreed in most cases with respective data of the original rock powder within the combined standard uncertainty of the method (2–3%), except the U concentration of BIR-1G, which showed a three times higher concentration compared to BIR-1.