New Reference Materials and Assessment of Matrix Effects for SIMS Measurements of Oxygen Isotopes in Garnet

Accurate ion microprobe analysis of oxygen isotope ratios in garnet requires appropriate reference materials to correct for instrumental mass fractionation that partly depends on the garnet chemistry (matrix effect). The matrix effect correlated with grossular, spessartine and andradite components was characterised for the Cameca IMS 1280HR at the SwissSIMS laboratory based on sixteen reference garnet samples. The correlations fit a second‐degree polynomial with maximum bias of ca. 4‰, 2‰ and 8‰, respectively. While the grossular composition range 0–25% is adequately covered by available reference materials, there is a paucity of them for intermediate compositions. We characterise three new garnet reference materials GRS2, GRS‐JH2 and CAP02 with a grossular content of 88.3 ± 1.2% (2s), 83.3 ± 0.8% and 32.5 ± 3.0%, respectively. Their micro scale homogeneity in oxygen isotope composition was evaluated by multiple SIMS sessions. The reference δ¹⁸O value was determined by CO₂ laser fluorination (δ¹⁸O_LF). GRS2 has δ¹⁸O_LF = 8.01 ± 0.10‰ (2s) and repeatability within each SIMS session of 0.30–0.60‰ (2s), GRS‐JH2 has δ¹⁸O_LF = 18.70 ± 0.08‰ and repeatability of 0.24–0.42‰ and CAP02 has δ¹⁸O_LF = 4.64 ± 0.16‰ and repeatability of 0.40–0.46‰.     

Diagenetic formation of gypsum and dolomite in a cold‐water coral mound in the Porcupine Seabight,off Ireland

Authigenic gypsum was found in a gravity core, retrieved from the top of Mound Perseverance, a giant cold‐water coral mound in the Porcupine Basin, off Ireland. The occurrence of gypsum in such an environment is intriguing, because gypsum, a classic evaporitic mineral, is undersaturated with respect to sea water. Sedimentological, petrographic and isotopic evidence point to diagenetic formation of the gypsum, tied to oxidation of sedimentary sulphide minerals (i.e. pyrite). This oxidation is attributed to a phase of increased bottom currents which caused erosion and enhanced inflow of oxidizing fluids into the mound sediments. The oxidation of pyrite produced acidity, causing carbonate dissolution and subsequently leading to pore‐water oversaturation with respect to gypsum and dolomite. Calculations based on the isotopic compositions of gypsum and pyrite reveal that between 21·6% and 28·6% of the sulphate incorporated into the gypsum derived from pyrite oxidation. The dissolution of carbonate increased the porosity in the affected sediment layer but promoted lithification of the sediments at the sediment‐water interface. Thus, authigenic gypsum can serve as a signature for diagenetic oxidation events in carbonate‐rich sediments. These observations demonstrate that fluid flow, steered by environmental factors, has an important effect on the diagenesis of coral mounds.     

Chemical and Isotopic Characteristics of the Kuroko‐Forming Volcanism

The Miocene northeast Honshu magmatic arc, Japan, formed at a terrestrial continental margin via a stage of spreading in a back‐arc basin (23–17 Ma) followed by multiple stages of submarine rifting (19–13 Ma). The Kuroko deposits formed during this period, with most forming during the youngest rifting stage. The mode of magma eruption changed from submarine basalt lava flows during back‐arc basin spreading to submarine bimodal basalt lava flows and abundant rhyolitic effusive rocks during the rifting stage. The basalts produced during the stage of back‐arc basin spreading are geochemically similar to mid‐ocean ridge basalt, with a depleted Sr–Nd mantle source, whereas those produced during the rifting stage possess arc signatures with an enriched mantle source. The Nb/Zr ratios of the volcanic rocks show an increase over time, indicating a temporal increase in the fertility of the source. The Nb/Zr ratios are similar in basalts and rhyolites from a given rift zone, whereas the Nd isotopic compositions of the rhyolites are less radiogenic than those of the basalts. These data suggest that the rhyolites were derived from a basaltic magma via crystal fractionation and crustal assimilation. The rhyolites associated with the Kuroko deposits are aphyric and have higher concentrations of incompatible elements than do post‐Kuroko quartz‐phyric rhyolites. These observations suggest that the aphyric rhyolite magma was derived from a relatively deep magma chamber with strong fractional crystallization. Almost all of the Kuroko deposits formed in close temporal relation to the aphyric rhyolite indicating a genetic link between the Kuroko deposits and highly differentiated rhyolitic magma.     

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.     

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.     

Dauphiné twinning and texture memory in polycrystalline quartz. Part 3: texture memory during phase transformation

Samples of quartz-bearing rocks were heated above the α (trigonal)–β (hexagonal) phase transformation of quartz (625–950°C) to explore changes in preferred orientation patterns. Textures were measured both in situ and ex situ with neutron, synchrotron X-ray and electron backscatter diffraction. The trigonal–hexagonal phase transformation does not change the orientation of c- and a-axes, but positive and negative rhombs become equal in the hexagonal β-phase. In naturally deformed quartzites measured by neutron diffraction a perfect texture memory was observed, i.e. crystals returned to the same trigonal orientation they started from, with no evidence of twin boundaries. Samples measured by electron back-scattered diffraction on surfaces show considerable twinning and memory loss after the phase transformation. In experimentally deformed quartz rocks, where twinning was induced mechanically before heating, the orientation memory is lost. A mechanical model can explain the memory loss but so far it does not account for the persistence of the memory in quartzites. Stresses imposed by neighboring grains remain a likely cause of texture memory in this mineral with a very high elastic anisotropy. If stresses are imposed experimentally the internal stresses are released during the phase transformation and the material returns to its original state prior to deformation. Similarly, on surfaces there are no tractions and thus texture memory is partially lost.     

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.     

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.     

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.