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.     

Diagenetic evolution of Aptian evaporites in the Namibe Basin (south‐west Angola)

The widespread and dissected nature of the Angolan gypsiferous salt residuals offers a uniquely detailed view of the lateral and vertical relations inherent to secondary evaporite textures, which typify exhumed salt masses worldwide. Such secondary textures are sometimes misinterpreted as primary evaporite textures. Thin, metre‐scale and patchy, dome‐like gypsum accumulations are well‐exposed within strongly incised present‐day river valleys along the eastern margin of the Namibe and Benguela basins (south‐west Angola). These sections are time equivalent to the main basinward subsurface evaporites (Aptian Loeme Formation) which mostly consist of halite. The gypsum (here called the Bambata Formation) is interpreted to represent the final residual product of fractional dissolution and recrystallization of the halite mass that occurred during Late Cretaceous margin uplift and continues today. This halite underwent multiple episodes of diagenetic alteration between its deposition and its final exhumation, leading to the formation of various secondary gypsum fabrics and solution‐related karst and breccia textures that typify the current evaporite outcrop. Four different diagenetic gypsum fabrics are defined: thinly bedded alabastrine, nodular alabastrine, displacive selenite rosettes and fibrous satin‐spar gypsum. Current arid conditions are responsible for a thin weathered crust developed at the top of the outcropping gypsum, but the fabrics in the main core of the current at‐surface evaporite unit mostly formed during the telogenetic stage of uplift prior to complete subaerial exposure. Alteration occurred as various dissolving and rehydrating saline minerals encountered shallow aquifers in the active phreatic and vadose zones. Geomorphological and petrographic analyses, mostly based on the cross‐cutting relations and crystallographic patterns in the outcrop, are used to propose a sequence of formation of these different fabrics.     

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.     

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.     

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.