High‐Precision Sr‐Nd‐Hf‐Pb Isotopic Composition of Chinese Geological Standard Glass Reference Materials CGSG‐1, CGSG‐2, CGSG‐4 and CGSG‐5 by MC‐ICP‐MS and TIMS

To assess the homogeneity of and provide the first Sr‐Nd‐Hf‐Pb isotopic reference values for the Chinese Geological Standard Glasses CGSG‐1, CGSG‐2, CGSG‐4 and CGSG‐5, we measured these isotopes in several measurement sessions over the course of nearly 3 years. The results were obtained by high‐precision MC‐ICP‐MS and TIMS. Our investigation indicates that these CGSG glass reference materials are homogenous with regard to Sr‐Nd‐Hf‐Pb isotopic distribution and are therefore suitable geochemical materials for Sr‐Nd‐Hf‐Pb isotope measurements. Clear differences in Sr‐Nd‐Hf‐Pb isotopic composition were observed between the glasses and the original powdered rock reference materials (CGSG‐2 and GSR‐7, and especially CGSG‐5 and GSR‐2) because of flux addition during preparation of the glasses. The new Sr‐Nd‐Hf‐Pb isotope data provided here might be useful to the geochemical community for in situ and bulk analysis.     

Accurate and Precise Silicon Isotope Analysis of Sulfur‐ and Iron‐Rich Samples by MC‐ICP‐MS

Silicon isotope determination of sulfur‐rich samples by MC‐ICP‐MS can be challenging because cation‐exchange chromatography used for Si purification does not efficiently remove anionic sulfur species. Results for pure Si standard solutions with addition of sulfate showed shifts of up to +1.04 ± 0.10‰ (2s) in δ³⁰Si. Doping of both standard solutions and samples with S to a fixed S/Si ratio can eliminate the relative change in instrumental mass fractionation due to variable S/Si in samples and also boosts the relative sensitivity of Si by up to 66%. Moreover, Fe hydroxide precipitation during sample processing adsorbs Si resulting in isotopic fractionations. Tests using Fe‐rich samples showed that this could be a major factor for observed shifts in δ³⁰Si. Acidification of the sample and standard solutions to a pH < 1 aggressively dissolved any Fe hydroxide precipitates, even in relatively Fe‐rich samples such as chondrite meteorites. The pH values of the sample solutions were subsequently adjusted to a range of 2–3 by adding ultra‐pure NaOH solutions. The combination of sulfur doping and the pH adjustment protocol ensured a full recovery of Si and proved to be an efficient and reliable method for Si isotope determination of S‐ and Fe‐rich materials.     

Determination of Platinum‐Group Elements and Re‐Os Isotopes using ID‐ICP‐MS and N‐TIMS from a Single Digestion after Two‐Stage Column Separation

We report an improved procedure for the determination of the platinum‐group elements (PGE) and Re, and Os isotopes from a single sample aliquot by isotope dilution (ID) using inductively coupled plasma‐mass spectrometry (ICP‐MS) and negative thermal ionisation mass spectrometry (N‐TIMS), respectively. A two‐stage column method was used to purify PGE‐Re from their sample matrix and interfering elements (e.g., Mo, Zr and Hf) after Os had been separated by CCl₄ solvent extraction. The first column separation step used cation exchange resin (AG50W‐X8) to concentrate PGE‐Re and some potential interfering elements (e.g., Mo, Zr and Hf). In the second step, N‐benzoyl‐N‐phenylhydroxylamine (BPHA) extraction resin was used to separate PGE‐Re from the remaining interfering elements, which all remained strongly absorbed to the resin. The method was used to determine the PGE and rhenium, and Os isotope ratios in a range of geochemical reference materials (TDB‐1, WGB‐1, BHVO‐2 and UB‐N). The obtained results agree well with those previously published. This new method enables PGE‐Re abundances and Os isotopic ratios to be determined on the same sample digestion, and circumvents the problems created by sample heterogeneity when comparing PGE and Re‐Os isotope data.     

Analytical solutions of linear finite‐ and small‐strain one‐dimensional consolidation

Analytical solutions are presented for linear finite‐strain one‐dimensional consolidation of initially unconsolidated soil layers with surcharge loading for both one‐ and two‐way drainage. These solutions complement earlier solutions for initially unconsolidated soil layers without surcharge and initially normally consolidated soil layers with surcharge. Small‐strain solutions for the consolidation of initially unconsolidated soil layers with surcharge loading are also presented, and the relationship between the earlier solutions for initially unconsolidated soil without surcharge and the corresponding small‐strain solutions, which was not addressed in the earlier work, is clarified. The new solutions for initially unconsolidated soil with surcharge loading can be applied to the analysis of low stress consolidation tests and to the partial validation of numerical solutions of non‐linear finite‐strain consolidation. They also clarify a formerly perplexing aspect of finite‐strain solution charts first noted in numerical solutions. Copyright © 2004 John Wiley & Sons, Ltd.     

In Situ U‐Th‐Pb Dating and Sr‐Nd Isotope Analysis of Bastnäsite by LA‐(MC)‐ICP‐MS

Bastnäsite is the end member of a large group of carbonate–fluoride minerals with the common formula (REE) CO₃F·CaCO₃. This group is generally widespread and, despite never occurring in large quantities, represents the major economic light rare earth element (LREE) mineral in deposits related to carbonatite and alkaline intrusions. Since bastnäsite is easily altered and commonly contains inclusions of earlier‐crystallised minerals, in situ analysis is considered the most suitable method to measure its U‐Th‐Pb and Sr‐Nd isotopic compositions. Electron probe microanalysis and laser ablation (multi‐collector) inductively coupled plasma‐mass spectrometry of forty‐six bastnäsite samples from LREE deposits in China, Pakistan, Sweden, Mongolia, USA, Malawi and Madagascar indicate that this mineral typically has high Th and LREE and moderate U and Sr contents. Analysis of an in‐house bastnäsite reference material (K‐9) demonstrated that precise and accurate U‐Th‐Pb ages could be obtained after common Pb correction. Moreover, the Th‐Pb age with its high precision is preferable to the U‐Pb age because most bastnäsites have relatively high Th rather than U contents. These results will have significant implications for understanding the genesis of endogenous ore deposits and formation processes related to metallogenic geochronology research.     

High‐Precision Fe and Mg Isotope Ratios of Silicate Reference Glasses Determined In Situ by Femtosecond LA‐MC‐ICP‐MS and by Solution Nebulisation MC‐ICP‐MS

In this study, a technique for high precision in situ Fe and Mg isotope determinations by femtosecond‐laser ablation‐multi collector‐ICP‐MS (fs‐LA‐MC‐ICP‐MS) was developed. This technique was employed to determine reference values for a series of common reference glasses that may be used for external standardisation of in situ Fe and Mg isotope determinations in silicates. The analysed glasses are part of the MPI‐DING and United States Geological Survey (USGS) reference glass series, consisting of basaltic (BIR‐1G, BCR‐2G, BHVO‐2G, KL2‐G, ML3B‐G) and komatiitic (GOR128‐G and GOR132‐G) compositions. Their Fe and Mg isotope compositions were determined by in situ fs‐LA‐MC‐ICP‐MS and by conventional solution nebulisation multi‐collector ICP‐MS. We determined δ⁵⁶Fe values for these glasses ranging between ‐0.04‰ and 0.10‰ (relative to IRMM‐014) and δ²⁶Mg values ranging between ‐0.40‰ and ‐0.15‰ (relative to DSM‐3). Our fs‐LA‐MC‐ICP‐MS results for both Fe and Mg isotope compositions agreed with solution nebulisation analyses within analytical uncertainties. Furthermore, the results of three USGS reference glasses (BIR‐1G, BHVO‐2G and BCR‐2G) agreed with previous results for powdered and dissolved aliquots of the same reference materials. Measurement reproducibilities of the in situ determinations of δ⁵⁶Fe and δ²⁶Mg values were usually better than 0.12‰ and 0.13‰ (2s), respectively. We further demonstrate that our technique is a suitable tool to resolve isotopic zoning in chemically‐zoned olivine crystals. It may be used for a variety of different applications on isotopically‐zoned minerals, e.g., in magmatic or metamorphic rocks or meteorites, to unravel their formation or cooling rates.     

First Multi‐Isotopic (Pb‐Nd‐Sr‐Zn‐Cu‐Fe) Characterisation of Dust Reference Materials (ATD and BCR‐723): A Multi‐Column Chromatographic Method Optimised to Trace Mineral and Anthropogenic Dust Sources

Atmospheric dust is an integral component of the Earth system with major implications for the climate, biosphere and public health. In this context, identifying and quantifying the provenance and the processes generating the various types of dust found in the atmosphere is paramount. Isotopic signatures of Pb, Nd, Sr, Zn, Cu and Fe are commonly used as sensitive geochemical tracers. However, their combined use is limited by the lack of (a) a dedicated chromatographic protocol to separate the six elements of interest for low‐mass samples and (b) specific reference materials for dust. Indeed, our work shows that USGS rock reference materials BHVO‐2, AGV‐2 and G‐2 are not applicable as substitute reference materials for dust. We characterised the isotopic signatures of these six elements in dust reference materials ATD and BCR‐723, representatives of natural and urban environments, respectively. To achieve this, we developed a specific procedure for dust, applicable in the 4–25 mg mass range, to separate the six elements using a multi‐column ion‐exchange chromatographic method and MC‐ICP‐MS measurements.     

Micromechanical viscoelasto‐plastic models and finite element implementation for rate‐independent and rate‐dependent permanent deformation of stone‐based materials

This paper presents parallel and serial viscoelasto‐plastic models to simulate the rate‐independent and the rate‐dependent permanent deformation of stone‐based materials, respectively. The generalized Maxwell viscoelastic and Chaboche's plastic models were employed to formulate the proposed parallel and serial viscoelasto‐plastic constitutive laws. The finite element (FE) implementation of the parallel model used a displacement‐based incremental formulation for the viscoelastic part and an elastic predictor—plastic corrector scheme for the elastoplastic component. The FE framework of the serial viscoelasto‐plastic model employed a viscoelastic predictor—plastic corrector algorithm. The stone‐based materials are consisted of irregular aggregates, matrix and air voids. This study used asphalt mixtures as an example. A digital sample was generated with imaging analysis from an optically scanned surface image of an asphalt mixture specimen. The modeling scheme employed continuum elements to mesh the effective matrix, and rigid bodies for aggregates. The ABAQUS user material subroutines defined with the proposed viscoelasto‐plastic matrix models were employed. The micromechanical FE simulations were conducted on the digital mixture sample with the viscoelasto‐plastic matrix models. The simulation results showed that the serial viscoelasto‐plastic matrix model generated more permanent deformation than the parallel one by using the identical material parameters and displacement loadings. The effect of loading rates on the material viscoelastic and viscoelasto‐plastic mixture behaviors was investigated. Permanent deformations under cyclic loadings were determined with FE simulations. The comparison studies showed that the simulation results correctly predicted the rate‐independent and rate‐dependent viscoelasto‐plastic constitutive properties of the proposed matrix models. Overall, these studies indicated that the developed micromechanical FE models have the abilities to predict the global viscoelasto‐plastic behaviors of the stone‐based materials. Copyright © 2009 John Wiley & Sons, Ltd.     

Elasto‐plastic modelling of stress‐path‐dependent behaviour of interfaces

A single‐surface elasto‐plastic model developed by Desai and his coworkers is used to predict the behaviour of an interface between sand and a steel plate. The loading in the experiments and in their predictions followed various stress and displacement paths. The results of predictions of the two‐ and three‐dimensional behaviour of the interface under both constant normal stress and constant normal stiffness conditions are presented. The predictions are compared with their corresponding experimental results. The model parameters were determined on the basis of 2‐D conventional experiments under the condition of constant normal stress and they were used in the prediction of the interface behaviour in various stress paths. There is, in general, a good agreement between the predicted and experimental results. Copyright © 2000 John Wiley & Sons, Ltd.     

A Synthetic Haematite Reference Material for LA‐ICP‐MS U‐Pb Geochronology and Application to Iron Oxide‐Cu‐Au Systems

In both nature and synthetic experiments, the common iron oxide haematite (α‐Fe₂O₃) can incorporate significant amounts of U into its crystal structure and retain radiogenic Pb over geological time. Haematite is a ubiquitous component of many ore deposit types and, therefore, represents a valuable hydrothermal mineral geochronometer, allowing direct constraints to be placed on the timing of ore formation and upgrading. However, to date, no suitable natural haematite reference material has been identified. Here, a synthetic haematite U‐Pb reference material (MR‐HFO) is characterised using LA‐ICP‐MS and ID‐TIMS. Centimetre‐scale ‘chips’ of synthesised α‐Fe₂O₃ were randomly microsampled via laser ablation‐extraction and analysed using ID‐TIMS. Reproducible U/Pb and Pb/Pb measurements were obtained across four separate chips (n = 13). Subsequently, an evaluation of the suitability MR‐HFO in constraining U‐Pb data via LA‐ICP‐MS is presented using a selection of natural samples ranging from Cenozoic to Proterozoic in age. The MR‐HFO normalised U‐Pb ratios are more concordant and ages more accurate versus the same LA‐ICP‐MS spot analyses normalised to zircon reference material, when compared with independently acquired ID‐TIMS data from the same natural haematite grains. Results establish MR‐HFO as a suitable reference material for LA‐ICP‐MS haematite U‐Pb geochronology.     

The major‐ and trace‐element whole‐rock fingerprints of Egyptian basalts and the provenance of Egyptian artefacts

Discrimination diagrams have been developed that source Egyptian basaltic artefacts using whole‐rock major element geochemistry. These include K₂O versus SiO₂, TiO₂ and P₂O₅ against MgO/Fe₂O₃^t (total Fe as Fe₂O₃), and a discriminant analysis diagram using SiO₂, Fe₂O₃^t, CaO, and MnO. A complementary set of diagrams uses easily obtained trace element data (Nb/Y versus Zr/Nb; Zr [ppm] versus Rb/Sr; TiO₂ [wt % volatile free] versus V; and Cr [ppm] versus Zr/Y) to determine the bedrock sources. These diagrams have been applied to seven First Dynasty basalt vessels (Abydos), two Fourth Dynasty basalt paving stones (Khufu's funerary temple, Giza), and two Fifth Dynasty paving stones (Sahure's complex, Abu Sir). They show that the bedrock source for all the artefacts was the Haddadin flow in northern Egypt. Multidimensional scaling and cluster analysis applied to the whole‐rock data (major elements and trace elements together) and previously published mineral fingerprinting studies confirm these results. Comparing mineral versus whole‐rock fingerprinting techniques, a major advantage of the former is the small sample size required (0.001 g compared to ≥ 0.1 g). Analytical costs are similar for both methods assuming that a comparison (bedrock) database can be assembled from the literature. For most archaeological problems, a whole‐rock bedrock database is more likely to exist than a mineral database, and whole‐rock analyses on artefacts will generally be easier to obtain than mineral analyses. Whole‐rock fingerprinting may be more sensitive than mineral‐based fingerprinting. Thus, if sample quantity is not an issue, whole‐rock analysis may have a slight cost, convenience, and technical advantage over mineral‐based methods. Our results also emphasize that the Egyptians cherished their Haddadin basalt flow and used it extensively and exclusively for manufacturing basalt vessels and paving stones for at least 600 years (∼3150 B.C. to 2500 B.C., approximate ages of the vessels and Abu Sir paving stones, respectively). © 2001 John Wiley & Sons, Inc.     

Platinum‐Group Element Results for Two Cobalt‐Rich Seamount Crust Ultra‐Fine Reference Materials: MCPt‐1and MCPt‐2

Two Co‐rich seamount crust reference materials, MCPt‐1 and MCPt‐2, were prepared using ultra‐fine particle size milling technique and characterised for the platinum‐group elements (PGEs). The raw material for these two reference materials was collected separately from the Magellan seamounts of the western Pacific Ocean and the seamounts of the central Pacific Ocean by Russian and Chinese scientists. First, they were ground by ball mill to a ?200 mesh powder, then further processed by ultra‐fine jet mill and well‐mixed. The particle size distributions of the samples were tested by a laser particle analyser; the average particle size was 1.8 and 1.5 μm (equal to about 2000 mesh) respectively. The homogeneity of six major and minor elements in these two materials was tested at the milligram level of sampling mass by high‐precision wavelength dispersive X‐ray fluorescence (XRF) spectrometry and at the microgram level of sampling mass by electron probe microanalyser. The homogeneity of more than forty trace elements, including Pt, was tested at the microgram level of sampling mass by LA‐ICP‐MS. Except for Rh, all PGEs were determined by isotope dilution‐ICP‐MS. Platinum in MCPt‐1 and MCPt‐2 was characterised as certified values, whereas the other five PGEs in MCPt‐1 and MCPt‐2 were reported as reference values. In addition, the information values of sixty‐two major, minor and trace elements were obtained by XRF, ICP‐AES and ICP‐MS. The minimum sampling mass for the determination of PGEs was 1 g, while the minimum sampling mass for the determination of the other elements was 2–5 mg.     

Determination of Trace Elements in Geological Reference Materials G‐3, GSP‐2 and SGD‐1a by Low‐Dilution Glass Bead Digestion and ICP‐MS

We present a revised alkali fusion method for the determination of trace elements in geological samples. Our procedure is based on simple acid digestion of powdered low‐dilution (flux : sample ≈ 2 : 1) glass beads where large sample dilution demanded by high total dissolved solids, a main drawback of conventional alkali fusion, could be circumvented. Three geological reference materials (G‐3 granite, GSP‐2 granodiorite and SGD‐1a gabbro) decomposed by this technique and routine tabletop acid digestion were analysed for thirty trace elements using a quadrupole ICP‐MS. Results by conventional acid digestion distinctly showed poor recoveries of Zr, Hf and rare earth elements due to incomplete dissolution of resistant minerals. On the other hand, results obtained by our method were in reasonable agreement with reference data for most analytes, indicating that refractory minerals were efficiently dissolved and volatile loss was insignificant.     

High Precision Sr‐Nd‐Hf‐Pb Isotopic Compositions of USGS Reference Material BCR‐2

The Lamont‐Doherty Earth Observatory radiogenic isotope group has been systematically measuring Sr‐Nd‐Pb‐Hf isotopes of USGS reference material BCR‐2 (Columbia River Basalt 2), as a chemical processing and instrumental quality control monitor for isotopic measurements. BCR‐2 is now a widely used geochemical inter‐laboratory reference material (RM), with its predecessor BCR‐1 no longer available. Recognising that precise and accurate data on RMs is important for ensuring analytical quality and for comparing data between different laboratories, we present a compilation of multiple digestions and analyses made on BCR‐2 during the first author's dissertation research. The best estimates of Sr, Nd and Hf isotope ratios and measurement reproducibilities, after filtering at the 2s level for outliers, were ⁸⁷Sr/⁸⁶Sr = 0.705000 ± 11 (2s, 16 ppm, n = 21, sixteen digestions, one outlier), ¹⁴³Nd/¹⁴⁴Nd = 0.512637 ± 13 (2s, 25 ppm, n = 27, thirteen digestions, one outlier) and ¹⁷⁶Hf/¹⁷⁷Hf = 0.282866 ± 11 (2s, 39 ppm, n = 25, thirteen digestions, no outliers). Mean Nd and Hf values were within error of those reported by Weis et al. (2006, 2007) in their studies of RMs; mean Sr values were just outside the 2s uncertainty range of both laboratories. Moreover, a survey of published Sr‐Nd‐Hf data shows that our results fall within the range of reported values, but with a smaller variability. Our Pb isotope results on acid leached BCR‐2 aliquots (n = 26, twelve digestions, two outliers) were ²⁰⁶Pb/²⁰⁴Pb = 18.8029 ± 10 (2s, 55 ppm), ²⁰⁷Pb/²⁰⁴Pb = 15.6239 ± 8 (2s, 52 ppm), ²⁰⁸Pb/²⁰⁴Pb = 38.8287 ± 25 (2s, 63 ppm). We confirm that unleached BCR‐2 powder is contaminated with Pb, and that sufficient leaching prior to digestion is required to achieve accurate values for the uncontaminated Pb isotopic compositions.     

Half‐a‐billion‐year‐old microscopic treasures—the Cambrian ‘Orsten’ fossils of Sweden

The creatures that gaze back at us through the binocular microscope are so uniquely well‐preserved and life‐like that had we not known better we would have thought that they were modern. Instead they are half‐a‐billion‐year‐old arthropods extracted from Cambrian rocks of Sweden. The microscopic fossils, colloquially known as the ‘Orsten’ fossils, are now world‐famous and basking in the light of the research catwalk since their discovery in the 1970s. These fossils have provided significant insight into the long lost Cambrian biotas and early animal evolution.     

Gilbert‐type deltas recording short‐term base‐level changes: Delta‐brink morphodynamics and related foreset facies

Gilbert‐type deltas are sensitive recorders of short‐term base‐level changes, but the delta‐front record of a base‐level rise tends to be erased by fluvial erosion during a subsequent base‐level fall, which renders the bulk record of base‐level changes difficult to decipher from the delta‐front deposits. The present detailed study of three large Pleistocene Gilbert‐type deltas uplifted on the southern coast of the Gulf of Corinth, Greece, indicates a genetic link between the delta‐front morphodynamic responses to base‐level changes and the delta‐slope sedimentation processes. Sigmoidal delta‐brink architecture signifies a base‐level rise and is accompanied by a debrite‐dominated assemblage of delta foreset deposits, thought to form when the aggrading delta front stores sediment and undergoes discrete gravitational collapses. Oblique delta‐brink architecture tends to be accompanied by a turbidite‐dominated assemblage of foreset deposits, which are thought to form when the delta‐front accommodation decreases and the sediment carried by hyperpycnal effluent bypasses the front. This primary signal of the system response to base‐level changes combines further with the secondary ‘noise’ of delta autogenic variation and possible allogenic fluctuations in fluvial discharge due to regional climatic conditions. Nevertheless, the evidence suggests that the facies trends of delta foreset deposits may be used to decipher the delta ‘hidden’ record of base‐level changes obliterated by fluvial topset erosion. Early‐stage bayhead deltas may be an exception from the hypothetical model, because their narrow front tends to be swept by river floods irrespective of base‐level behaviour and their subaqueous slope deposits are thus mainly turbidites.