激光剥蚀-等离子体质谱技术及其在地球化学宇宙化学和环境研究中的应用

激光剥蚀-等离子体质谱(LA-ICPMS)已成为地球化学、宇宙化学和环境研究领域元素和同位素原位分析最重要的技术之一。文章介绍了多种类型的质谱仪及其使用的激光器。用途最广的LA-ICPMS仪器之一是单接收器扇形磁场质谱仪,配有Nd:YAG激光剥蚀系统(激光波长分为193 nm和213 nm两种),MPI Mainz实验室使用的就是这套系统,文章对此作一详细介绍。文中阐述了数据优化技术及其多种校正过程;介绍LA-ICPMS在痕量元素和同位素分析领域的一些应用,包括参考物质的研制,Hawaiian玄武岩、Martian陨石、生物骨针和珊瑚虫中痕量元素分析及熔融包裹体和富钙-铝碳质球粒陨石中的铅和锶同位素测量。     

Palaeoglaciation of Bayan Har Shan,northeastern Tibetan Plateau: glacial geology indicates maximum extents limited to ice cap and ice field scales

Key locations within an extensive area of the northeastern Tibetan Plateau, centred on Bayan Har Shan, have been mapped to distinguish glacial from non‐glacial deposits. Prior work suggests palaeo‐glaciers ranging from valley glaciers and local ice caps in the highest mountains to a regional or even plateau‐scale ice sheet. New field data show that glacial deposits are abundant in high mountain areas in association with large‐scale glacial landforms. In addition, glacial deposits are present in several locations outside areas with distinct glacial erosional landforms, indicating that the most extensive palaeo‐glaciers had little geomorphological impact on the landscape towards their margins. The glacial geological record does indicate extensive maximum glaciation, with local ice caps covering entire elevated mountain areas. However, absence of glacial traces in intervening lower‐lying plateau areas suggests that local ice caps did not merge to form a regional ice sheet on the northeastern Tibetan Plateau around Bayan Har Shan. No evidence exists for past ice sheet glaciation. Copyright © 2009 John Wiley & Sons, Ltd.     

Naturally occurring asbestos in eastern Australia: a review of geological occurrence,disturbance and mesothelioma risk

Potential asbestos-bearing rocks account for about 0.2% of the land area of eastern Australia. The main mode of occurrence is as narrow cross fibre and slip fibre veins of chrysotile asbestos in serpentinised ophiolite complexes along the boundaries of major tectonic domains. Smaller deposits of chrysotile and amphibole asbestos occur in metamorphosed mafic and ultramafic rocks associated with the Macquarie Volcanic Arc in New South Wales. Amphibole asbestos is also known from Proterozoic and Palaeozoic amphibolite and from Devonian basalt. Natural asbestos-bearing materials in eastern Australia have been disturbed by mining, road construction, agriculture and forestry, urban development and through natural weathering processes. Persons most at risk of potential exposure to asbestos from natural sources include: farmers who work or live in areas where asbestos-bearing materials may be routinely disturbed by agricultural activities; construction workers involved in large-scale earthwork projects in areas underlain by asbestos-bearing rocks; and quarry workers who unwittingly disturb asbestos-bearing materials. Government authorities and private enterprise need to take geological factors into account to reduce the likelihood of unplanned disturbance of natural asbestos-bearing materials. Electronic supplementary material  The online version of this article (doi:) contains supplementary material, which is available to authorized users.     

Trace Element Data for Gold, Iridium and Silver in Seventy Geochemical Reference Materials

New concentrations for Au, Ir and Ag obtained by instrumental neutron activation analysis are presented for seventy geochemical reference materials. Results in agreement with literature values for Au and Ir down to concentrations of a few ng g⁻¹ were obtained. For Au and Ir concentrations above 10 ng g⁻¹, the repeatability of replicate analyses of reference materials was mostly better than 10%. For concentrations between 1 and 10 ng g⁻¹ the RSD for Ir was 10–30%, whereas for Au it was higher and more variable (20–50%). In addition, concentrations for Cd and Hg are presented for some of the same reference materials. The high RSD at relatively high concentrations seen in gold for some RMs (e.g., WMG-1, WMS-1) did not exist for Ir and suggests homogeneity for this platinum-group element at the sub-sample size used in this study. For the following eight RMs, mostly ultramafic rocks (CHR-Pt+, OREAS-13P, OREAS-14P, PCC-1, UMT-1, WMG-1, WMS-1, WPR-1), Ir measurements agreed within ± 10% of mostly certified or recommended concentrations, which ranged from 2 ng g⁻¹ to 6 μg g⁻¹. For the reference material UB-N, iridium concentration compared favourably to published results obtained by isotope dilution ICP-MS methods and a previously unrecognised heterogeneity is inferred for Au, Hg and Sb, but not for the other measured elements.     

Array performances for ambient vibrations on a shallow structure and consequences over <Emphasis Type="Italic">V</Emphasis><Subscript><Emphasis Type="Italic">s</Emphasis></Subscript> inversion

Valuable information about one-dimensional soil structures can be obtained by recording ambient vibrations at the surface, in which the energy contribution of surface waves predominates over the one of other types of waves. The dispersion characteristics of surface waves allow the retrieval of the shear-wave velocity as a function of depth. Microtremor studies are usually divided in two stages: deriving the dispersion (or auto-correlation) curve from the recorded signals and inverting it to obtain the site velocity profile. The possibility to determine the dispersion curve over the adequate frequency range at one site depends on the array aperture and on the wavefield spectra amplitude that can be altered by filtering effects due to the ground structure. Microtremors are usually recorded with several arrays of various apertures to get the spectral curves over a wide frequency band, and different methods also exist for processing the raw signals. With the objective of defining a strategy to achieve reliable results for microtremor on a shallow structure, we analyse synthetic ambient vibrations (vertical component) simulated with 333 broadband sources for a 25-m deep soil layer overlying a bedrock. The first part of our study is focused on the determination of the reliable frequency range of the spectral curves (dispersion or auto-correlation) for a given array geometry. We find that the wavenumber limits deduced from the theoretical array re sponse are good estimates of the valid spectral curve range. In the second part, the spectral curves are calculated with the three most popular noise-processing techniques (frequency–wavenumber, high-resolution frequency–wavenumber and spa tial auto-correlation methods) and inverted indi vidually in each case. The inversions are performed with a tool based on the neighbour hood algorithm that offers a better estimation of the global uncertainties than classical linearised methods, especially if the solution is not unique. Several array apertures are necessary to construct the dispersion (auto-correlation) curves in the appropriate frequency range. Considering the final velocity profiles, the three tested methods are almost equivalent, and no significant advantage was found for one particular method. With the chosen model, all methods exhibit a penetration limited to the bedrock depth, as a consequence of the filtering effect of the ground structure on the vertical component, which was observed in numerous shallow sites.     

Probability distributions for maximum wave and crest heights

The paper discusses short- and long-term probability models of ocean waves. The Gaussian theory is reviewed, and nonlinear short-term probability distributions are derived from a narrow band second-order model. The nonlinearity has different impact on different measurement techniques, and this is further demonstrated for wave data from the WAVEMOD Crete measurement campaign and laser data from the North Sea. Finally, we give some examples on how the short-term statistics may be used to estimate the probability distributions for the maximum waves during individual storms as well as in a wave climate described by long-term distributions.     

The timing and extent of the eruption of the Siberian Traps large igneous province: Implications for the end-Permian environmental crisis

We present new high-precision ⁴⁰Ar/³⁹Ar ages on feldspar and biotite separates to establish the age, duration and extent of the larger Siberian Traps volcanic province. Samples include basalts and gabbros from Noril'sk, the Lower Tunguska area on the Siberian craton, the Taimyr Peninsula, the Kuznetsk Basin, Vorkuta in the Polar Urals, and from Chelyabinsk in the southern Urals. Most of the ages, except for those from Chelyabinsk, are indistinguishable from those found at Noril'sk. Cessation of activity at Noril'sk is constrained by a ⁴⁰Ar/³⁹Ar age of 250.3 ± 1.1 Ma for the uppermost Kumginsky Suite.The new ⁴⁰Ar/³⁹Ar data confirm that the bulk of Siberian volcanism occurred at 250 Ma during a period of less than 2 Ma, extending over an area of up to 5 million km². The resolution of the data allows us to confidently conclude that the main stage of volcanism either immediately predates, or is synchronous with, the end-Permian mass extinction, further strengthening an association between volcanism and the end-Permian crisis. A sanidine age of 249.25 ± 0.14 Ma from Bed 28 tuff at the global section and stratotype at Meishan, China, allows us to bracket the P–Tr boundary to 0.58 ± 0.21 myr, and enables a direct comparison between the ⁴⁰Ar/³⁹Ar age of the Traps and the Permo–Triassic boundary section.Younger ages (243 Ma) obtained for basalts from Chelyabinsk indicate that volcanism in at least the southern part of the province continued into the Triassic.     

Study of water tension differences in heterogeneous sandy soils using surface ERT

Herbaceous vegetation in the Sahel grows almost exclusively on sandy soils which preferentially retain water through infiltration and storage. The hydrological functioning of these sandy soils during rain cycles is unknown. One way to tackle this issue is to spatialize variations in water content but these are difficult to measure in the vadose zone. We investigated the use of Electrical Resistivity Tomography (ERT) as a technique for spatializing resistivity in a non-destructive manner in order to improve our knowledge of relevant hydrological processes. To achieve this, two approaches were examined. First, we focused on a possible link between water tension (which is much easier to measure in the field by point measurements than water content), and resistivity (spatialized with ERT). Second, because ERT is affected by solution non-uniqueness and reconstruction smoothing, we improved the accuracy of ERT inversion by comparing calculated solutions with in-situ resistivity measurements. We studied a natural microdune during a controlled field experiment with artificial sprinkling which reproduced typical rainfall cycles. We recorded temperature, water tension and resistivity within the microdune and applied surface ERT before and after the 3 rainfall cycles. Soil samples were collected after the experiment to determine soil physical characteristics. An experimental relationship between water tension and water content was also investigated. Our results showed that the raw relationship between calculated ERT resistivity and water tension measurements in sand is highly scattered because of significant spatial variations in porosity. An improved correlation was achieved by using resistivity ratio and water tension differences. The slope of the relationship depends on the soil solution conductivity, as predicted by Archie's law when salted water was used for the rain simulation. We found that determining the variations in electrical resistivity is a sensitive method for spatializing the differences in water tension which are directly linked with infiltration and evaporation/drainage processes in the vadose zone. However, three factors complicate the use of this approach. Firstly, the relation between water tension and water content is generally non-linear and dependent on the water content range. This could limit the use of our site-specific relations for spatializing water content with ERT through tension. Secondly, to achieve the necessary optimization of ERT inversion, we used destructive resistivity measurements in the soil, which renders ERT less attractive. Thirdly, we found that the calculated resistivity is not always accurate because of the smoothing involved in surface ERT data inversion. We conclude that further developments are needed into ERT image reconstruction before water tension (and water content) can be spatialized in heterogeneous sandy soils with the accuracy needed to routinely study their hydrological functioning.     

The Caulerpa racemosa invasion: a critical review

Caulerpa racemosa var. cylindracea is a marine Chlorophyta introduced into the Mediterranean Sea from south-western Australia. Since 1990, it has been invading the Mediterranean Sea and the Canary Islands, raising ecological problems. Although this invasion event can be considered as one of the most serious in the history of species introduced into the Mediterranean Sea, C. racemosa has not triggered as much attention as the famous "killer alga"Caulerpa taxifolia. The aim of the present study was: (i) to summarize the current state of knowledge with regard to the distribution, the various biological and ecological characteristics of the introduced C. racemosa and its impact on the Mediterranean coastal environment; (ii) to discuss the various hypotheses regarding the explanation for its rapid and successful spread; (iii) to investigate the disparity in the treatment of C. racemosa and Caulerpa taxifolia invasions; and (iv) to outline future research needs.     

The Correlation Structure of Matheron's Classical Variogram Estimator Under Elliptically Contoured Distributions

The classical variogram estimator proposed by Matheron can be written as a quadratic form of the observations. When data have an elliptically contoured distribution with constant mean, the correlation between the classical variogram estimator at two different lags is a function of the spatial design matrix, the covariance matrix, and the kurtosis. Several specific cases are studied closely. A subclass of elliptically contoured distributions with a particular family of covariance matrices is shown to possess exactly the same correlation structure for the classical variogram estimator as the multivariate independent Gaussian distribution. The consequences on variogram fitting by generalized least squares are discussed.