Description: Highlights • Hydrothermal basaltic glass alterations were performed in various salinity solutions. • Increased salinity strongly enhances initial dissolution rates of basaltic glass. • Rates are extrapolated at lower temperature to be applied on natural estuaries. • Si and K fluxes for several days of reaction are comparable to river inputs to the Oceans. • Other elements fluxes are several orders of magnitude lower than global river inputs. In order to better constrain the geochemical budget of Si in the ocean, and potentially other elements released by the dissolution of silicates, the alteration of riverine particulate material in estuaries and seawater needs to be estimated. For this, a series of alteration experiments of basaltic glass were performed at various degrees of salinity (from 0 to 3.5gL−1) in far-from-equilibrium conditions. The solution used is a filtered natural seawater standard from the Atlantic Ocean. The forward dissolution rates increase from 2.1 ·10−7molSim−2s−1(S=0gL−1) to 7.7 ·10−7molSim−2s−1(S=3.5gL−1) at 90◦C and were extrapolated at 16◦C (from 2.9 ·10−10molSim−2s−1at S=0gL−1to 1.1 ·10−9molSim−2s−1at S=3.5gL−1). This positive relationship between glass dissolution rate and salinity degree is consistent with published investigations concerning the role of specific cations and ligands present in seawater, which can promote dissolution at the glass surface. These results illustrate the potential of river basaltic glass particles to dissolve quickly in the water column after entering into the brackish waters of estuaries, and before sinking on continental margins. Based on these dissolution rates and on assumptions on the particulate solid flux of fresh basaltic glass exported by rivers towards the ocean, the corresponding flux of dissolved Si is estimated to range between 2 and 8 ·1012molSiyr−1. This is of the same order of magnitude as the estimated river dissolved Si flux, which represents therefore a significant input of Si into the ocean. Additionally, if the glass dissolution process remains congruent during the residence time of suspended particles into the water column, the K flux to the ocean could also be significantly affected.

Description: Chemical weathering plays an important role in sequestering atmospheric CO2, but its potential influence on global climate over geological timescales remains debated. To some extent, this uncertainty arises from the difficulty in separating the respective contribution of sedimentary and crystalline silicate rocks to past weathering rates in the geological record; two types of rocks having presumably different impact on the long-term carbon cycle. In this study, we investigate the use of rare earth element (REE) and neodymium isotopes (εNd) in leached iron oxide fractions of river sediments for tracing the origin of weathered rocks on continents. A new index, called ‘concavity index’ (CI), is defined for measuring the degree of mid-REE enrichment in geological samples, which enables the determination of the source of iron oxides in sediments, such as seawater-derived Fe-oxyhydroxide phases, ancient marine Fe oxides derived from the erosion of sedimentary rocks, and recent secondary oxides formed in soils via alteration of crystalline silicate rocks or pyrite oxidation. Using this index, we demonstrate that the εNd difference between paired Fe-oxide and detrital fractions in river sediments (defined here as ∆εNd Feox-Det) directly reflects the relative contribution of sedimentary versus crystalline silicate rocks during weathering. While rivers draining old cratons and volcanic provinces display near-zero ∆εNd Feox-Det values indicative of dominant silicate weathering (0.5 ± 1.1; n = 30), multi-lithological catchments hosting sedimentary formations yield systematically higher values (2.7 ± 1.2; n = 44), showing that sedimentary rock weathering can be traced by the occurrence of riverine Fe oxides having more radiogenic Nd isotope signatures compared to detrital fractions. This assumption is reinforced by the evidence that calculated ∆εNd Feox-Det values agree well with previous estimates for carbonate and silicate weathering rates in large river basins. Examining the influence of climate and tectonics on measured Nd isotopic compositions, we find that ∆εNd Feox-Det is strongly dependent on temperature in lowlands, following an Arrhenius-like relationship that reflects enhanced alteration of silicate rocks and formation of secondary Fe oxides in warmer climates. In contrast, in high-elevation catchments, ∆εNd Feox-Det defines striking correlation with maximum basin elevation, which we also interpret as reflecting the intensification of silicate weathering and associated Fe oxide formation as elevation decreases, due to the combined effects of thicker soils and warmer temperature. Overall, our new findings are consistent with previous assertions that the alteration of sedimentary rocks prevails in high-elevation environments, while silicate weathering dominates in floodplains. This novel approach combining REE and Nd isotopes opens new perspectives for disentangling the weathering signals of sedimentary and crystalline silicate rocks in the geologic record, which could be used in future studies to reassess the causal relationships between mountain uplift, erosion and climate throughout Earth's history.

Description: This contribution aims to report the reflections we had with the scientific community during two international workshops on reference materials for stable isotopes in Davos (2002) and Nice (2003). After evaluating the isotopic homogeneity of some existing reference materials, based on either certificates, literature data or specific inter-laboratory rounds, we confirm these as primary reference materials or propose new ones relative to which stable isotope compositions should be reported. We propose DSM-3 for Mg, NIST SRM 915a for Ca, L-SVEC for Li and NBS28 for Si. Cadmium does not yet have a well identified delta zero material, although three commercial mono-elemental Cd solutions have yielded the same isotopic composition relative to one another. In order to scale the linearity of any mass spectrometer, some secondary reference materials are also proposed: Cambridge-1 solution for Mg, the “Münster-Cd” and JEPPIM Cd solutions for Cd and the “Big Batch” silicate for Si. The team from Nancy propose to prepare a mixed spike solution for Li isotopes. Well-characterised natural samples such as ocean or continental waters, diatoms, sponges, rocks and minerals are needed to validate the entire analytical procedure, particularly to take into account the effect of sample mineralisation and of chemical manipulations for elemental separation prior to analysis.