Applications of clumped-isotope palaeothermometry

Standard palaeotemperature equations, used to interpret the formation conditions of carbonate materials, are generally problematic. This is due to the need to know both the δ18O value of the water and the precipitated carbonate to complete the equation. The clumped-isotope method overcomes these uncertainties by examining the affinity of heavy isotopes bonding (13C18O16O = 47CO2) in favour of bonding to lighter isotopes (12C16O16O = 44CO2) in evolved CO2 from carbonates. This process of “clumping” is sensitive to ambient temperature, so can be used to determine palaeotemperature, but is independent of bulk isotopic composition of the original water. Measured values (Δ47) are expressed as per mil variation of the relative abundance of an isotopologue compared to the theoretical predicted relative abundance based on a stochastic random distribution. This study reports the first set of clumped-isotope results from the University of Wollongong laboratory. Improvements were made to previously developed analytical systems to more accurately and precisely determine carbonate formation temperatures. This study has indicated that the cold-water carbonate glendonite and equilibrium precipitated cave deposits have the potential to be utilised as reliable clumped isotope palaeotemperature proxies. Further improvements in the clumped isotope method are needed to more accurately investigate both of these types of material as well to resolve the origin of discrepancies in the mollusc clumpedisotope results

3806Ma Isua rhyolites and dacites affected by low temperature Eoarchaean surficial alteration: Earth's earliest weathering

This paper reports evidence for Earth's oldest-recognised low temperature alteration, at ~3800. Ma. Potassic felsic schists with a protolith age of 3806 ± 2. Ma form a ~30. km long unit in the amphibolite facies, deformed, Isua supracrustal belt (West Greenland). At a single locality, boudinaged layers (nodules) within the schists are low strain zones: they are fine-grained, weakly feldspar-phyric, contain quartz amygdules and have fiamme-like structures, all supporting a volcanic protolith.The nodules and surrounding schistose matrix contain abundant, 100-50μm, euhedral, oscillatory zoned 3806Ma zircons. The rare earth patterns of the zircons indicate crystallisation was magmatic. Some zircons contain axial lobate voids indicating that they grew at low pressure as the magma exsolved a fluid. Ti-in-zircon thermometry indicates crystallisation temperatures of 750-650°C. Taken together, these zircon features indicates growth at eutectic temperatures in a hypabyssal chamber as the magma was exsolving a fluid phase. The magmatic zircons have e{open}Hf initial values of ~0 and δ18OVSMOW of +5.0‰ (Hiess et al., 2009), showing that the source of the volcanic rocks was devoid of assimilated markedly older or weathered crustal material, and probably essentially juvenile. In contrast, the whole rock δ18OVSMOW values are elevated at +14.7 to +16.2‰, indicative of superimposed low-temperature alteration processes.The nodules and matrix schists have non-igneous bulk compositions, exemplified by strong enrichment in K2O and depletion in Na2O. They are depleted in Sr, have no negative Eu anomalies, but have high Rb/Sr, with an Rb-Sr age of 3760±140Ma (Jacobsen and Dymek, 1988). This indicates that the alteration involving strong degradation of plagioclase occurred in the Eoarchaean. Trace element compositions and establishment of alteration vectors suggest the protoliths were likely rhyolitic and dacitic in composition.The strongest-modified matrix schist compositions contain biotite±calcite±dolomite with increase in MgO relative to the nodules, which indicates early magnesian carbonate growth. The whole-rock chemistry, decoupling of the igneous zircon and whole-rock oxygen isotope signatures and the Rb-Sr dating indicate that after eruption, the 3806Ma felsic volcanic rocks underwent Eoarchaean low-temperature potassic alteration with weathering and groundwater circulation the most likely process. The geochemistry of the Isua felsic schists is compared with that of better-preserved volcanic rocks where the alteration conditions are known. This suggests a subaerial environment. The carbonatisation of the Isua felsic schists demonstrates drawdown of atmospheric CO2 into rocks made porous by the weathering

InterCarb: A Community Effort to Improve Interlaboratory Standardization of the Carbonate Clumped Isotope Thermometer Using Carbonate Standards

International audienceIncreased use and improved methodology of carbonate clumped isotope thermometry has greatly enhanced our ability to interrogate a suite of Earth-system processes. However, interlaboratory discrepancies in quantifying carbonate clumped isotope (Δ47) measurements persist, and their specific sources remain unclear. To address interlaboratory differences, we first provide consensus values from the clumped isotope community for four carbonate standards relative to heated and equilibrated gases with 1,819 individual analyses from 10 laboratories. Then we analyzed the four carbonate standards along with three additional standards, spanning a broad range of δ47 and Δ47 values, for a total of 5,329 analyses on 25 individual mass spectrometers from 22 different laboratories. Treating three of the materials as known standards and the other four as unknowns, we find that the use of carbonate reference materials is a robust method for standardization that yields interlaboratory discrepancies entirely consistent with intralaboratory analytical uncertainties. Carbonate reference materials, along with measurement and data processing practices described herein, provide the carbonate clumped isotope community with a robust approach to achieve interlaboratory agreement as we continue to use and improve this powerful geochemical tool. We propose that carbonate clumped isotope data normalized to the carbonate reference materials described in this publication should be reported as Δ47 (I-CDES) values for Intercarb-Carbon Dioxide Equilibrium Scale

Modelling the Ohmic L-mode ramp-down phase of JET hybrid pulses using JETTO with Bohm-gyro-Bohm transport

The empirical Bohmgyro-Bohm (BgB) transport model implemented in the JETTO code is used to predictively simulate the purely Ohmic (OH), L-mode current-ramp-down phase of three JET hybrid pulses, which combine two different ramp rates with two different electron densities (at the beginning of the ramp). The modelling is discussed, namely the strategy to reduce as much as possible the number of free parameters used to benchmark the model predictions against the experimental results. Hence, keeping the gas puffing rate as measured whilst controlling the line-averaged electron density via the recycling coefficient (which in the modelling is taken at the separatrix instead of the wall), one of the many possible ways to fix the total particle source, it is shown that the BgB model reproduces well the experimental data, as far as both average quantities (plasma internal inductance and volume-averaged electron temperature) and profiles (electron density and temperature) are concerned, with relative errors remaining mostly below 20%. The sensitivenesses with respect to the recycling coefficient, the ion effective charge, the energy of neutrals entering the plasma through the separatrix and the need to introduce a particle pinch are assessed; the necessity for a proper sawtooth model if experimental results are to be reproduced is also shown. The strong non-linear coupling in a OH plasma between density, temperature and current (essentially via interplay between the powerbalance equation, Joules heating with a temperature-dependent resistivity and the dependence of BgB transport coefficients on profile gradients) is put in evidence and analyzed in light of modelling results. It is still inferred from the modelling that the real value of the recycling coefficient at the separatrix (basically, the so-called fuelling efficiency times the actual recycling coefficient at the wall) must become close to one in the final stages of the discharges, when the gas puffing is switched off and so recycling comes to be the only source of particles. If the wall recycling remains close to one (as standard for tokamaks), this may indicate that the fuelling efficiency also approaches unity, apparently consistent with the observed fact that the plasma is pushed towards the machine wall at the end of the current ramps