Chemical Characterisation of the USGS Reference Glasses GSA-1G, GSC-1G, GSD-1G, GSE-1G, BCR-2G, BHVO-2G and BIR-1G Using EPMA, ID-TIMS, ID-ICP-MS and LA-ICP-MS

The USGS reference glasses GSA-1G, GSC-1G, GSD-1G, GSE-1G, BCR-2G, BHVO-2G and BIR-1G were investigated by different analytical techniques. All these materials have a geological (basaltic) matrix and are therefore useful in igneous geochemistry as matrix-matched reference materials for microanalytical techniques. The new GS glasses have trace elements in groups at concentration levels of about < 0.01, 5, 50 and 500 μg g^-1. Their major element compositions have been determined by EPMA, and trace elements have been analysed by LA-ICP-MS and two isotope dilution techniques using TIMS and ICP-MS. EPMA and LA-ICP-MS analyses indicated that the USGS reference glasses are homogeneous at the μm to mm scale with respect to major (variations < 1-2%) and most trace elements (variations 1-4%). Trace element data obtained from the different analytical techniques agreed within an uncertainty of 1-5%, indicating that between method results are comparable. Therefore, the preliminary working values for the four USGS GS glasses calculated from these data have a low level of uncertainty.     

Suitability of Mn‐ and Fe‐Rich Reference Materials for Microanalytical Research

Manganese‐ and iron‐rich materials are of major geoscientific and economic interest, many of which contain microscopic features that provide valuable information. To obtain accurate results, a homogeneous microanalytical reference material for calibration is needed. Several researchers have used the Mn‐ and Fe‐rich RMs, JMn‐1, NOD‐A‐1, NOD‐P‐1 and FeMn‐1, for this purpose; therefore, they were tested in this study to determine their suitability for microanalysis. Their homogeneity was investigated by laser ablation‐inductively coupled plasma‐mass spectrometry (LA‐ICP‐MS) with two different types of lasers (nano‐ and femtosecond), with spot and line scan analyses and with different operating parameters, such as spot size, pulse repetition rate and fluence. As the established manganese nodule RMs revealed inhomogeneities for picogram to microgram test portions, we also investigated the new synthetic Fe‐ and Mn‐rich RM, FeMnOx‐1. FeMnOx‐1 was found to be homogeneous for large (ø 40 μm: 2% RSD repeatability) and small (ø 8–10 μm: 10% RSD repeatability) spot sizes. This homogeneity is in the range of the homogeneous NIST SRM 610 and GSE‐1G reference glasses. Furthermore, FeMnOx‐1 revealed a large‐scale homogeneity within uncertainties of a few per cent, using test portions in the ng range, when measuring four individual mounts of this material.     

Quaternary thermokarst and thermal erosion features in northern France: origin and palaeoenvironments

A thermokarst is a collapse feature resulting from the thawing of ice‐rich permafrost or of massive ice of various origins. Little attention has been paid to the sedimentary fabric resulting from this type of collapse, except for glaciotectonic features. In western Europe, two palaeo‐forms are commonly studied: lithalsas and ice‐wedge casts. Collapsed pingos are much rarer. Very few papers have compiled present‐day and fossil data. Here, field data collected from quarries in the eastern Paris Basin were analysed, providing useful records of thermokarst collapses in alluvial calcareous silts, sands, and gravels. These forms have a circular shape when viewed on satellite images. Permafrost is attested regionally by the recurrent occurrence of meter‐sized pattern grounds at the surface of the chalk and of ice‐wedge casts. Traces of segregation and reticulate ice are common. These features are primarily connected to a major interstadial, c. 150 ka BP, orbitally forced and commonly associated with a major glacial retreat. They occur both in drained and waterlogged situations, resulting in a specific pattern of deformation. They are controlled by the brittle and plastic behaviour of sediments and resemble passive glaciotectonism. Normal and reverse faults, with the offset decreasing downward, are common, and those with local shear are reported. Lithalsas, seasonal frost blisters, spring frost blisters and perhaps pingos seem to have formed. Most of these deformations correspond to thermokarst sinkholes bordered by gravitational collapse faults. The offset of these faults increases towards the surface, and the faults have been recurrently confused with neotectonism triggered by palaeo‐earthquakes. However, there are no faults beneath the observed deformation features, and the region lacks recorded seismic activity over the last century. Our data may be helpful in interpreting similar structures elsewhere.     

Neogene desertification of Africa

Throughout the Neogene, the faunas and floras in Africa recorded global climatic changes. We present an overview of Neogene desertification in Africa by tracing stable isotopes in eggshells and mammalian enamel, by faunal (changes in hypsodonty, etc.) and floral changes in sequences at the latitudinal extremities of the continent and the equator. This work reveals that desertification started in the southwest ca 17–16 Ma, much earlier than the region of the present-day Sahara (ca 8–7 Ma) and long before the deserts in East Africa (Plio-Pleistocene). A consequence of this history is that animals and plants inhabiting the South of the continent had a long period of time in which to adapt to arid, unstable climatic conditions. When parts of East Africa became arid during the Late Miocene and Plio-Pleistocene, several of these lineages expanded northwards and occupied developing arid niches before local lineages could adapt. Several of the latter became extinct, while others withdrew westwards as the tropical forest diminished in extent. It is proposed that the history of desertification in Africa was related to that of the polar ice caps (Antarctic, Arctic).     

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。     

Oxygen isotopic compositions of chondrules: Implications for evolution of oxygen isotopic reservoirs in the inner solar nebula

We review the oxygen isotopic compositions of minerals in chondrules and compound objects composed of a chondrule and a refractory inclusion, and bulk oxygen isotopic compositions of chondrules in unequilibrated ordinary, carbonaceous, enstatite, and Kakangari-like chondrites, focusing on data acquired using secondary ion mass-spectrometry and laser fluorination coupled with mass-spectrometry over the last decade. Most ferromagnesian chondrules from primitive (unmetamorphosed) chondrites are isotopically uniform (within 3–4‰ in Δ¹⁷O) and depleted in ¹⁶O (Δ¹⁷O>−7‰) relative to amoeboid olivine aggregates (AOAs) and most calcium–aluminum-rich inclusions (CAIs) (Δ¹⁷O<−20‰), suggesting that these classes of objects formed in isotopically distinct gaseous reservoirs, ¹⁶O-poor and ¹⁶O-rich, respectively. Chondrules uniformly enriched in ¹⁶O (Δ¹⁷O<−15‰) are exceptionally rare and have been reported only in CH chondrites. Oxygen isotopic heterogeneity in chondrules is mainly due to the presence of relict grains. These appear to consist of chondrules of earlier generations and rare refractory inclusions; with rare exceptions, the relict grains are ¹⁶O-enriched relative to chondrule phenocrysts and mesostasis. Within a chondrite group, the magnesium-rich (Type I) chondrules tend to be ¹⁶O-enriched relative to the ferrous (Type II) chondrules. Aluminum-rich chondrules in ordinary, enstatite, CR, and CV chondrites are generally ¹⁶O-enriched relative to ferromagnesian chondrules. No systematic differences in oxygen isotopic compositions have been found among these chondrule types in CB chondrites. Aluminum-rich chondrules in carbonaceous chondrites often contain relict refractory inclusions. Aluminum-rich chondrules with relict CAIs have heterogeneous oxygen isotopic compositions (Δ¹⁷O ranges from −20‰ to 0‰). Aluminum-rich chondrules without relict CAIs are isotopically uniform and have oxygen isotopic compositions similar to, or approaching, those of ferromagnesian chondrules. Phenocrysts and mesostases of the CAI-bearing chondrules show no clear evidence for ¹⁶O-enrichment compared to the CAI-free chondrules. Spinel, hibonite, and forsterite of the relict refractory inclusions largely retained their original oxygen isotopic compositions. In contrast, plagioclase and melilite of the relict CAIs experienced melting and ¹⁶O-depletion to various degrees, probably due to isotopic exchange with an ¹⁶O-poor nebular gas. Several igneous CAIs experienced isotopic exchange with an ¹⁶O-poor nebular gas during late-stage remelting in the chondrule-forming region. On a three-isotope diagram, bulk oxygen isotopic compositions of most chondrules in ordinary, enstatite, and carbonaceous chondrites plot above, along, and below the terrestrial fractionation line, respectively. Bulk oxygen isotopic compositions of chondrules in altered and/or metamorphosed chondrites show evidence for mass-dependent fractionation, reflecting either interaction with a gaseous/fluid reservoir on parent asteroids or open-system thermal metamorphism. Bulk oxygen isotopic compositions of chondrules and oxygen isotopic compositions of individual minerals in chondrules and refractory inclusions from primitive chondrites plot along a common line of slope of 1, suggesting that only two major reservoirs (gas and solids) are needed to explain the observed variations. However, there is no requirement that each had a permanently fixed isotopic composition. The absolute (²⁰⁷Pb–²⁰⁶Pb) and relative (²⁷Al–²⁶Mg) chronologies of CAIs and chondrules and the differences in oxygen isotopic compositions of most chondrules (¹⁶O-poor) and most refractory inclusions (¹⁶O-rich) can be interpreted in terms of isotopic self-shielding during UV photolysis of CO in the initially ¹⁶O-rich (Δ¹⁷O−25‰) parent molecular cloud or protoplanetary disk. According to these models, the UV photolysis preferentially dissociates C¹⁷O and C¹⁸O in the parent molecular cloud and in the peripheral zones of the protoplanetary disk. If this process occurs in the stability field of water ice, the released atomic ¹⁷O and ¹⁸O are incorporated into water ice, while the residual CO gas becomes enriched in ¹⁶O. During the earliest stages of evolution of the protoplanetary disk, the inner solar nebula had a solar H₂O/CO ratio and was ¹⁶O-rich. During this time, AOAs and the ¹⁶O-rich CAIs and chondrules formed. Subsequently, the inner solar nebula became H₂O- and ¹⁶O-depleted, because ice-rich dust particles, which were depleted in ¹⁶O, agglomerated outside the snowline (5 AU), drifted rapidly towards the Sun and evaporated. During this time, which may have lasted for 3 Myr, most chondrules and the ¹⁶O-depleted igneous CAIs formed. We infer that most chondrules formed from isotopically heterogeneous, but ¹⁶O-depleted precursors, and experienced isotopic exchange with an ¹⁶O-poor nebular gas during melting. Although the relative roles of the chondrule precursor materials and gas–melt isotopic exchange in establishing oxygen isotopic compositions of chondrules have not been quantified yet, mineralogical, chemical, and isotopic evidence indicate that Type I chondrules may have formed in chemical and isotopic equilibrium with nebular gas of variable isotopic composition. Whether these variations were spatial or temporal are not known yet.     

Holocene salt‐marsh sedimentary infilling and relative sea‐level changes in West Brittany (France) using foraminifera‐based transfer functions

In order to reconstruct former sea‐levels and to better characterize the history of Holocene salt‐marsh sedimentary infillings in West Brittany (western France), local foraminifera‐based transfer functions were developed using weighted‐average‐partial‐least‐squares (WAPLS) regression, based on a modern data set of 26 and 51 surface samples obtained from salt‐marshes in the bay of Tresseny and the bay of Brest, respectively. Fifty cores were retrieved from Tresseny, Porzguen, Troaon and Arun salt‐marshes, which were litho‐ and biostratigraphically analysed in order to reconstruct palaeoenvironmental changes. A total of 26 AMS ¹⁴C age determinations were performed within the sediment successions. The Holocene evolution of salt‐marsh environments can be subdivided into four stages: (i) a development of brackish to freshwater marshes (from c. 6400 to 4500 cal. a BP); (ii) salt‐marsh formation behind gravel barriers in the bay of Brest (from 4500 to 2900 cal. a BP); (iii) salt‐marsh erosion and rapid changes of infilling dynamics due to the destruction of coastal barriers by storm events (c. 2900?2700 cal. a BP); (iv) renewed salt‐marsh deposition and small environmental changes (from 2700 cal. a BP to present). From the application of transfer functions to fossil assemblages, 14 new sea‐level index points were obtained, indicating a mean relative sea‐level rise of around 0.90±0.12 mm a^?1 since 6300 cal. a BP.     

Nickeliferous pyrite tracks pervasive hydrothermal alteration in Martian regolith breccia: A study in NWA 7533

Martian regolith breccia NWA 7533 (and the seven paired samples) is unique among Martian meteorites in showing accessory pyrite (up to 1% by weight). Pyrite is a late mineral, crystallized after the final assembly of the breccia. It is present in all of the lithologies, i.e., the fine‐grained matrix (ICM), clast‐laden impact melt rocks (CLIMR), melt spherules, microbasalts, lithic clasts, and mineral clasts, all lacking magmatic sulfides due to degassing. Pyrite crystals show combinations of cubes, truncated cubes, and octahedra. Polycrystalline clusters can reach 200 μm in maximum dimensions. Regardless of their shape, pyrite crystals display evidence of very weak shock metamorphism such as planar features, fracture networks, and disruption into subgrains. The late fracture systems acted as preferential pathways for partial replacement of pyrite by iron oxyhydroxides interpreted as resulting from hot desert terrestrial alteration. The distribution and shape of pyrite crystals argue for growth at moderate to low growth rate from just‐saturated near neutral (6 < pH<10), H₂S‐HS‐rich fluids at minimum log fO₂ of >FMQ + 2 log units. It is inferred from the maximum Ni contents (4.5 wt%) that pyrite started crystallizing at 400–500 °C, during or shortly after a short‐duration, relatively low temperature, thermal event that lithified and sintered the regolith breccias, 1.4 Ga ago as deduced from disturbance in several isotope systematics.     

Monitoring the effects of disposal of fine sediments from maintenance dredging on suspended particulate matter concentration in the Belgian nearshore area (southern North Sea)

The impact of continuous disposal of fine-grained sediments from maintenance dredging works on the suspended particulate matter concentration in a shallow nearshore turbidity maximum was investigated during dredging experiment (port of Zeebrugge, southern North Sea). Before, during and after the experiment monitoring of SPM concentration using OBS and ADV altimetry was carried out at a location 5 km west of the disposal site. A statistical analysis, based on the concept of populations and sub-sampling, was applied to evaluate the effect. The data revealed that the SPM concentration near the bed was on average more than two times higher during the dredging experiment. The disposed material was mainly transported in the benthic layer and resulted in a long-term increase of SPM concentration and formation of fluid mud layers. The study shows that SPM concentration can be used as an indicator of environmental changes if representative time series are available.