A Common Reference Material for Cadmium Isotope Studies – NIST SRM 3108

Research into natural mass‐dependent stable isotope fractionation of cadmium has rapidly expanded in the past few years. Methodologies are diverse with MC‐ICP‐MS favoured by all but one laboratory, which uses thermal ionisation mass spectrometry (TIMS). To quantify the isotope fractionation and correct for instrumental mass bias, double‐spike techniques, sample‐calibrator bracketing or element doping has been used. However, easy comparison between data sets has been hampered by the multitude of in‐house Cd solutions used as zero‐delta reference in different laboratories. The lack of a suitable isotopic reference material for Cd is detrimental for progress in the long term. We have conducted a comprehensive round‐robin assay of NIST SRM 3108 and the Cd isotope offsets to commonly used in‐house reference materials. Here, we advocate NIST SRM 3108 both as an isotope standard and the isotopic reference point for Cd and encourage its use as ‘zero‐delta’ in future studies. The purity of NIST SRM 3108 was evaluated regarding isobaric and polyatomic molecular interferences, and the levels of Zn, Pd and Sn found were not significant. The isotope ratio ¹¹⁴Cd/¹¹⁰Cd for NIST SRM 3108 lies within ～ 10 ppm Da^?1 of best estimates for the Bulk Silicate Earth and is validated for all measurement technologies currently in use.     

GGR Biennial Critical Review: Analytical Developments Since 2014

This GGR biennial critical review covers developments and innovations in key analytical methods published since January 2014, relevant to the chemical, isotopic and crystallographic characterisation of geological and environmental materials. In nine selected analytical fields, publications considered to be of wide significance are summarised, background information is provided and their importance evaluated. In addition to instrumental technologies, this review also presents a summary of new developments in the preparation and characterisation of rock, microanalytical and isotopic reference materials, including a précis of recent changes and revisions to ISO guidelines for reference material characterisation and reporting. Selected reports are provided of isotope ratio determinations by both solution nebulisation MC‐ICP‐MS and laser ablation‐ICP‐MS, as well as of radioactive isotope geochronology by LA‐ICP‐MS. Most of the analytical techniques elaborated continue to provide new applications for geochemical analysis; however, it is noted that instrumental neutron activation analysis has become less popular in recent years, mostly due to the reduced availability of nuclear reactors to act as a neutron source. Many of the newer applications reported here provide analysis at increasingly finer resolution. Examples include atom probe tomography, a very sensitive method providing atomic scale information, nanoscale SIMS, for isotopic imaging of geological and biological samples, and micro‐XRF, which has a spatial resolution many orders of magnitude smaller than conventional XRF.     

Zircon U-Pb geochronology and geochemistry of Late Devonian–Carboniferous granitoids in NW Iran: implications for the opening of Paleo-Tethys

ABSTRACT

We present zircon U-Pb crystallization ages combined with bulk rock major and trace element geochemistry and Sr-Nd-Pb and zircon in-situ Hf isotopic compositions of the Amand and Moro granitoid intrusions in northwest Iran. The Amand and Moro plutons include granite and syeno-diorite with LA-ICP-MS U-Pb zircon ages of 367 ± 6.8 Ma and 351 ± 1.3 Ma, respectively, representative of Late Devonian-Early Carboniferous magmatic activity in NW Iran. Geochemical characteristics such as typical enrichments in alkalis, Nb, Zr, Ga and Y, depletion in P and Sr and fractionated REE patterns with high Ga/Al ratios and Eu negative anomalies are consistent with A-type magmatic signatures. The granitoids are classified as A₂-type and within-plate granitoids. The bulk rock geochemistry (enrichments in Th, Nb and, high Th/Yb, Zr/Y ratios) along with low variation of ¹⁴³Nd/¹⁴⁴Nd_(i) and ⁸⁷Sr/⁸⁶Sr_(i) ratios and positive zircon εHf_(t) support the role of a mantle plume component for the evolution of the Amand and Moro A-type granitoids in an extensional tectonic environment. In fitting with wider regional knowledge, this magmatism occurred during Paleo-Tethys opening in northern Gondwana.     

Geochronology of the Xihuashan Tungsten Deposit in Southeastern China: Constraints from Re–Os and U–Pb Dating

Xihuashan tungsten deposit is one of the earliest explored tungsten deposits in southeastern China. It is a vein type deposit genetically associated with the Xihuashan granite pluton. Here we report new dating and zircon geochemistry results. Re–Os isotopic dating for molybdenite intergrowth with wolframite in the oldest generation of the Xihuashan pluton yielded an isochron age of 157.0 ± 2.5 Ma (2σ). Zircon U–Pb laser ablation inductively coupled plasma mass spectrometry (LA‐ICP‐MS) dating shows that the pluton crystallized at 155.7 ± 2.2 Ma (2σ). This age is similar to the molybdenite Re–Os age for the ore deposit within error. This, together with published data, suggests that the major W(Mo)‐Sn mineralization occurred between 160–150 Ma in southeastern China. These deposits constitute a major part of the magmatic‐metallogenic belt of eastern Nanlin. The lower Re content in molybdenite of the Xihuashan tungsten deposit shows crustal origin for the ore‐forming material. The limited direct contributions from the subducting slab for the tungsten mineralization in the Nanling region suggest a change of the style of the paleo‐Pacific plate beneath southeastern China.     

Exploring the impact of diagenesis on (isotope) geochemical and microstructural alteration features in biogenic aragonite

For the Quaternary and Neogene, aragonitic biogenic and abiogenic carbonates are frequently exploited as archives of their environment. Conversely, pre‐Neogene aragonite is often diagenetically altered and calcite archives are studied instead. Nevertheless, the exact sequence of diagenetic processes and products is difficult to disclose from naturally altered material. Here, experiments were performed to understand biogenic aragonite alteration processes and products. Shell subsamples of the bivalve Arctica islandica were exposed to hydrothermal alteration. Thermal boundary conditions were set at 100°C, 175°C and 200°C. These comparably high temperatures were chosen to shorten experimental durations. Subsamples were exposed to different ¹⁸O‐depleted fluids for durations between two and twenty weeks. Alteration was documented using X‐ray diffraction, cathodoluminescence, fluorescence and scanning electron microscopy, as well as conventional and clumped isotope analyses. Experiments performed at 100°C show redistribution and darkening of organic matter, but lack evidence for diagenetic alteration, except in Δ₄₇ which show the effects of annealing processes. At 175°C, valves undergo significant aragonite to calcite transformation and neomorphism. The δ¹⁸O signature supports transformation via dissolution and reprecipitation, but isotopic exchange is limited by fluid migration through the subsamples. Individual growth increments in these subsamples exhibit bright orange luminescence. At 200°C, valves are fully transformed to calcite and exhibit purple‐blue luminescence with orange bands. The δ¹⁸O and Δ₄₇ signatures reveal exchange with the aqueous fluid, whereas δ¹³C remains unaltered in all experiments, indicating a carbonate‐buffered system. Clumped isotope temperatures in high‐temperature experiments show compositions in broad agreement with the measured temperature. Experimentally induced alteration patterns are comparable with individual features present in Pleistocene shells. This study represents a significant step towards sequential analysis of diagenetic features in biogenic aragonites and sheds light on reaction times and threshold limits. The limitations of a study restricted to a single test organism are acknowledged and call for refined follow‐up experiments.     

Flow dynamics at the origin of thin clayey sand lacustrine turbidites: Examples from Lake Hazar,Turkey

Turbidity currents and their deposits can be investigated using several methods, i.e. direct monitoring, physical and numerical modelling, sediment cores and outcrops. The present study focused on thin clayey sand turbidites found in Lake Hazar (Turkey) occurring in eleven clusters of closely spaced thin beds. Depositional processes and sources for three of those eleven clusters are studied at three coring sites. Bathymetrical data and seismic reflection profiles are used to understand the specific geomorphology of each site. X‐ray, thin sections and CT scan imagery combined with grain‐size, geochemical and mineralogical measurements on the cores allow characterization of the turbidites. Turbidites included in each cluster were produced by remobilization of surficial slope sediment, a process identified in very few studies worldwide. Three types of turbidites are distinguished and compared with deposits obtained in flume studies published in the literature. Type 1 is made of an ungraded clayey silt layer issued from a cohesive flow. Type 2 is composed of a partially graded clayey sand layer overlain by a mud cap, attributed to a transitional flow. Type 3 corresponds to a graded clayey sand layer overlain by a mud cap issued from a turbulence‐dominated flow. While the published experimental studies show that turbulence is damped by cohesion for low clay content, type 3 deposits of this study show evidence for a turbulence‐dominated mechanism despite their high clay content. This divergence may in part relate to input variables, such as water chemistry and clay mineralogy, that are not routinely considered in experimental studies. Furthermore, the large sedimentological variety observed in the turbidites from one coring site to another is related to the evolution of a sediment flow within a field‐scale basin made of a complex physiography that cannot be tackled by flume experiments.     

Barium Isotopic Compositions in Thirty‐Four Geological Reference Materials Analysed by MC‐ICP‐MS

Measurement of Ba isotope ratios of widely available reference materials is required for interlaboratory comparison of data. Here, we present new Ba isotope data for thirty‐four geological reference materials, including silicates, carbonates, river/marine sediments and soils. These reference materials (RMs) cover a wide range of compositions, with Ba mass fractions ranging from 6.4 to 1900 µg g^?1, SiO₂ from 0.62% to 90.36% m/m and MgO from 0.08% to 41.03% m/m. Accuracy and precision of our data were assessed by the analyses of duplicate samples and USGS rock RMs. Barium isotopic compositions for all RMs were in agreement with each other within uncertainty. The variation of δ^138/134Ba in these RMs was up to 0.7‰. The shale reference sample, affected by a high degree of chemical weathering, had the highest δ^138/134Ba (0.37 ± 0.03‰), while the stream sediment obtained from a tributary draining carbonate rocks was characterised by the lowest δ^138/134Ba (?0.30 ± 0.05‰). Geochemical RMs play a fundamental role in the high‐precision and accurate determination of Ba isotopic compositions for natural samples with similar matrices. Analyses of these RMs could provide universal comparability for Ba isotope data and enable assessment of accuracy for interlaboratory data.     

Pennsylvanian carbonate platforms adjacent to deltaic systems in an active marine foreland basin (Escalada Fm., Cantabrian Zone,NW Spain)

The Pennsylvanian marine foreland basin of the Cantabrian Zone (NW Spain) is characterized by the unique development of kilometre‐size and hundred‐metre‐thick carbonate platforms adjacent to deltaic systems. During Moscovian time, progradational clastic wedges fed by the orogen comprised proximal alluvial conglomerates and coal‐bearing deltaic sequences to distal shelfal marine deposits associated with carbonate platforms (Escalada Fm.) and distal clay‐rich submarine slopes. A first phase of carbonate platform development (Escalada I, upper Kashirian‐lower Podolskian) reached a thickness of 400 m, nearly 50 km in width and developed a distal high‐relief margin facing a starved basin, nearly 1000‐m deep. Carbonate slope clinoforms dipped up to 30° and consisted of in situ microbial boundstone, pinching out downslope into calciturbidites, argillaceous spiculites and breccias. The second carbonate platform (Escalada II, upper Podolskian‐lower Myachkovian) developed beyond the previous platform margin, following the basinward progradation of siliciclastic deposits. Both carbonate platforms include: (1) a lower part composed of siliciclastic‐carbonate cyclothems characterized by coated‐grain and ooid grainstones; and (2) a carbonate‐dominated upper part, composed of tabular and mound‐shaped wackestone and algal‐microbial boundstone strata alternating at the decametre scale with skeletal and coated‐grain grainstone beds. Carbonate platforms initiated in distal sectors of the foreland marine shelf during transgressions, when terrigenous sediments were stored in the proximal part, and developed further during highstands of 3rd‐order sequences in a high‐subsidence context. During the falling stage and lowstand systems tracts, deltaic systems prograded across the shelf burying the carbonate platforms. Key factors involved in the development of these unique carbonate platforms in an active foreland basin are: (1) the large size of the marine shelf (approaching 200 km in width); (2) the subsidence distribution pattern across the marine shelf, decreasing from proximal shoreline to distal sectors; (3) Pennsylvanian glacio‐eustacy affecting carbonate lithofacies architecture; and (4) the environmental conditions optimal for fostering microbial and algal carbonate factories.     

Runoff and sediment yield from land under various uses in a Mediterranean mountain area: long‐term results from an experimental station

In this study we analyzed runoff and sediment yield from land under various traditional and current land uses in Mediterranean mountain areas, using long‐term data from an experimental station in the Aísa Valley, Central Spanish Pyrenees. Monitoring at this station has provided 20 years of data that can help explain the hydrological and geomorphological changes that have been observed at larger spatial scales, and also the changes that have occurred to some of the most characteristic landscapes of the Mediterranean middle mountains. In spite of the problems associated with the use of small experimental plots, the results obtained are consistent with other studies in the Mediterranean region, and confirm the strong influence of land use changes on runoff generation and sediment yield. The results indicate that: (i) cereal cultivation on steep slopes (both alternating cereal cultivation and fallow on sloping fields and shifting agriculture on the steepest slopes) represents a major problem for soil conservation. This explains the occurrence throughout the Mediterranean mountains of many degraded hillslopes, which show evidence of sheet wash erosion, rilling, gullying and shallow landsliding; (ii) farmland abandonment has led to a marked reduction in runoff and sediment yield as a consequence of rapid plant recolonization, particularly by dense shrubs; (iii) the natural transformation of abandoned fields into grazing meadows has reduced runoff and sediment yield. Land use trends in the Mediterranean mountains are mainly characterized by generalized farmland abandonment and a decrease in livestock pressure. From a hydrological and geomorphological point of view the main consequences have been a reduction in overland flow from the hillslopes, and a reduction in sediment sources, with differences up to one order of magnitude in sediment yield from dense shrub cover and grazing meadow areas compared with areas under shifting agriculture. Copyright © 2012 John Wiley & Sons, Ltd.     

Strong ground motion record selection for the reliable prediction of the mean seismic collapse capacity of a structure group

How to select a limited number of strong ground motion records (SGMRs) is an important challenge for the seismic collapse capacity assessment of structures. The collapse capacity is considered as the ground motion intensity measure corresponding to the drift‐related dynamic instability in the structural system. The goal of this paper is to select, from a general set of SGMRs, a small number of subsets such that each can be used for the reliable prediction of the mean collapse capacity of a particular group of structures, i.e. of single degree‐of‐freedom systems with a typical behaviour range. In order to achieve this goal, multivariate statistical analysis is first applied, to determine what degree of similarity exists between each selected small subset and the general set of SGMRs. Principal Component analysis is applied to identify the best way to group structures, resulting in a minimum number of SGMRs in a proposed subset. The structures were classified into six groups, and for each group a subset of eight SGMRs has been proposed. The methodology has been validated by analysing a first‐mode‐dominated three‐storey‐reinforced concrete structure by means of the proposed subsets, as well as the general set of SGMRs. The results of this analysis show that the mean seismic collapse capacity can be predicted by the proposed subsets with less dispersion than by the recently developed improved approach, which is based on scaling the response spectra of the records to match the conditional mean spectrum. Copyright © 2010 John Wiley & Sons, Ltd.