In situ Lithium and Boron isotope determinations in mica, pyroxene, and serpentine by LA-MC-ICP-MS

Boron and Li are light, incompatible elements that preferentially partition into the liquid phase, whether melt or aqueous fluid, and thus are useful for tracking fluid-related processes in rocks. Most of the Li isotopic data presently available on subduction-related rocks are from whole-rock analyses; and the B isotopic analyses of subduction material have been carried out either on whole-rocks or in-situ on an accessory phase, such as tourmaline. The new method presented here couples an ESI New Wave UP-193-FX ArF* (193 nm) excimer laser-ablation microscope with a Neptune Plus (Thermo Scientific) MC-ICP-MS aiming to measure both Li and B isotopes in situ with good spatial resolution (metamorphic minerals are commonly chemically zoned, and whole-rock analyses lose this detail). The data thus obtained are compared with SIMS analyses on the same mineral samples for B, and with MC-ICP-MS analyses on whole-rock or mineral separates from the same sample for Li. Additionally, data acquired on tourmaline standards were compared to SIMS values. The results show that for B concentrations above 5 μg/g, the data obtained by LA-MC-ICP-MS and by SIMS are identical within error, for mica (phengitic muscovite), pyroxene (jadeite), serpentine (antigorite), and tourmaline. For Li concentrations above 10 μg/g, the data obtained by LA-MC-ICP-MS and by MC-ICP-MS are also identical, within error, for mica (phengitic muscovite), and pyroxene (jadeite). However, analyses of tourmaline standards have shown significant differences with reference values, so LA-MC-ICP-MS does not yet appear to be an appropriate method to analyze Li isotopes in tourmalines. Thus, LA-MC-ICP-MS is a suitable method to measure Li and B isotopes with good spatial resolution in major rock-forming silicates from subduction-related rocks where concentrations exceed 10 μg/g and 5 μg/g, respectively, with an error on individual measurements equal to or less than previously used methods, but obtainable in a significantly shorter amount of time. The external reproducibility is ± 2.88 to 3.31 ‰ for B and ± 1.50 to 1.75 for Li, which is lower than or equal to the variations encountered within a given chemically zoned sample (up to 10 ‰ of variation within a given natural sample).

Comparison and validation of physical wave parameterizations in spectral wave models

Recent developments in the physical parameterizations available in spectral wave models have already been validated, but there is little information on their relative performance especially with focus on the higher order spectral moments and wave partitions. This study concentrates on documenting their strengths and limitations using satellite measurements, buoy spectra, and a comparison between the different models. It is confirmed that all models perform well in terms of significant wave heights; however higher-order moments have larger errors. The partition wave quantities perform well in terms of direction and frequency but the magnitude and directional spread typically have larger discrepancies. The high-frequency tail is examined through the mean square slope using satellites and buoys. From this analysis it is clear that some models behave better than the others, suggesting their parameterizations match the physical processes reasonably well. However none of the models are entirely satisfactory, pointing to poorly constrained parameterizations or missing physical processes. The major space-time differences between the models are related to the swell field stressing the importance of describing its evolution. An example swell field confirms the wave heights can be notably different between model configurations while the directional distributions remain similar. It is clear that all models have difficulty in describing the directional spread. Therefore, knowledge of the source term directional distributions is paramount in improving the wave model physics in the future.

On the stability and spatiotemporal variance distribution of salinity in the upper ocean

Despite recent advances in ocean observing arrays and satellite sensors, there remains great uncertainty in the large-scale spatial variations of upper ocean salinity on the interannual to decadal timescales. Consonant with both broad-scale surface warming and the amplification of the global hydrological cycle, observed global multidecadal salinity changes typically have focussed on the linear response to anthropogenic forcing but not on salinity variations due to changes in the static stability and or variability due to the intrinsic ocean or internal climate processes. Here, we examine the static stability and spatiotemporal variability of upper ocean salinity across a hierarchy of models and reanalyses. In particular, we partition the variance into time bands via application of singular spectral analysis, considering sea surface salinity (SSS), the Brunt Väisälä frequency (N2), and the ocean salinity stratification in terms of the stabilizing effect due to the haline part of N2 over the upper 500m. We identify regions of significant coherent SSS variability, either intrinsic to the ocean or in response to the interannually varying atmosphere. Based on consistency across models (CMIP5 and forced experiments) and reanalyses, we identify the stabilizing role of salinity in the tropics—typically associated with heavy precipitation and barrier layer formation, and the role of salinity in destabilizing upper ocean stratification in the subtropical regions where large-scale density compensation typically occurs.