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).

A comparison of in situ vs. ex situ filtration methods on the assessment of dissolved and particulate metals at hydrothermal vents

The objective of this study was to assess the impact of the filtration method (in situ vs. ex situ) on the dissolved/particulate partitioning of 12 elements in hydrothermal samples collected from the Lucky Strike vent field (Mid-Atlantic Ridge; MAR). To do so, dissolved ( <0.45 mu m) and particulate Mg, Li, Mn, U, V, As, Ba, Fe, Zn, Cd, Pb and Cu were measured using different techniques (HR-ICP-MS, ICP-AES and CCSA). Using in situ filtration as a baseline, we showed that ex situ filtration (on-board and on shore after freezing) resulted in an underestimation of the dissolved pool, which was counterbalanced by an overestimation of the particulate pool for almost all the elements studied. We also showed that on-board filtration was acceptable for the assessment of dissolved and particulate Mn, Mg, Li and U for which the measurement bias for the dissolved fraction did not exceed 3%. However, in situ filtration appeared necessary for the accurate assessment of the dissolved and particulate concentrations of V, As, Fe, Zn, Ba, Cd, Pb and Cu. In the case of Fe, on-board filtration underestimated the dissolved pool by up to 96%. Laboratory filtration (after freezing) resulted in a large bias in the dissolved and particulate concentrations, unambiguously discounting this filtration method for deep-sea chemical speciation studies. We discuss our results in light of the precipitation processes that can potentially affect the accuracy of ex situ filtration methods.

Dissolved inorganic carbon budgets in the eastern subpolar North Atlantic in the 2000s from in situ data

The subpolar North Atlantic (SPNA) is important in the global carbon cycle because of the deep water ventilation processes that lead to both high uptake of atmospheric CO2 and large inventories of anthropogenic CO2 (C-ant). Thus, it is crucial to understand its response to increasing anthropogenic pressures. In this work, the budgets of dissolved inorganic carbon (DIC), C-ant and natural DIC (DICnat) in the eastern SPNA in the 2000s, are jointly analyzed using in situ data. The DICnat budget is found to be in steady state, confirming a long-standing hypothesis from in situ data for the first time. The biological activity is driving the uptake of natural CO2 from the atmosphere. The C-ant increase in the ocean is solely responsible of the DIC storage rate which is explained by advection of C-ant from the subtropics (65%) and C-ant air-sea flux (35%). These results demonstrate that the C-ant is accumulating in the SPNA without affecting the natural carbon cycle.

Mean structure of the North Atlantic subtropical permanent pycnocline from in-situ observations

In the north Atlantic subtropical gyre, the oceanic vertical structure of density is characterized by a region of rapid increase with depth. This layer is called the permanent pycnocline. The permanent pycnocline is found below a surface mode water ,which are ventilated every winter when penetrated locally by the mixed layer. Assessing the structure and variability of the permanent pycnocline is of a major interest in the understanding of the climate system because the pycnocline layer delimits important heat and anthropogenic reservoir. Moreover, the heat content structure translate into changes in the large scale stratification feature, such as the permanent pycnocline. We developed a new objective algorithm for the characterization of the large scale structure of the permanent pycnocline (OAC-P). Argo data have been used with OAC-P to provide a detailed description of the mean structure of the North-Atlantic subtropical pycnocline (e.g.: depth, thickness, temperature, salinity, density, potential vorticity). Results reveal a surprisingly complex structure with inhomogeneous properties. While the classical bowl shape of the pycnocline depth is captured, much more complex pycnocline structure emerges at the regional scale. In the southern recirculation gyre of the Gulf Stream Extension, the pycnocline is deep, thick, the maximum of stratification is found in the middle on the layer and follow an isopycnal surface. But local processes influence and modify this textbook description and the pycnocline is characterized by a vertically asymmetric structure and gradients in thermohaline properties. T/S distribution along the permanent pycnocline depth is complex and reveals a diversity of water masses resulting from mixing of different source waters. We will present the observed mean structure of the North-Atlantic subtropical permanent pycnocline and relate it to physical processes that constraint it.

IQuOD 4th workshop in Tokyo: Copernicus Marine in situ TAC, a service for operational oceanography

Copernicus is a European system for monitoring the Earth. COPERNICUS-CMEMS products and services are meant to serve all marine applications: Marine resources, Maritime safety, Coastal and Marine Environment, Seasonal Forecast & Climate. The service is ambitious as the ocean is complex and many processes are involved, from physical oceanography, biology, geology, ocean-atmosphere fluxes, solar radiations, moon induced tides, anthropic activity. A multi-platform approach is essential, taking into account sea-level stations, coastal buoys, HF radars, river flows, drifting buoys, sea-mammal or fishes fitted with sensors, vessels, gliders, floats.