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Biogenic carbonate minerals are widely used as archives in paleoenvironmental research, providing substantial information for past depositional and diagenetic regimes. However, nearly all biogenic carbonates undergo post-mortem diagenetic alteration to variable degrees. Diagenetic features are essentially caused by complex fluid-solid interaction including recrystallization and neomorphosis of shell architecture and related geochemical resetting. A common conception is that a given primary shell texture is replaced by a secondary fabric via micro-scale dissolution-reprecipitation reactions that may reach geochemical and/or isotopic equilibrium with the diagenetic fluid. Here we document that the process of petrographic and geochemical alteration of a biogenic carbonate archive progresses stepwise, and the re-equilibration processes can be separated in space and time. More specifically, attached and bound aqueous fluids within the shell organic matter and fluid inclusions likely play a crucial role in the early stages of alteration within a relatively rock-buffered system. Degradation of organics was observed via decreased sulfur concentration and decreased fluorescence. In this early stage of alteration, the conversion of micro-scale aragonite biominerals to metastable diagenetic calcite (meso)crystals is documented by RAMAN spectroscopy, electron backscatter diffraction (EBSD), and a decrease in strontium concentrations. Further stabilization to larger, neomorphosed calcite crystals resulted from re-equilibration with external fluids and was evidenced by EBSD, oxygen isotope data, and further reduction of strontium. Spatial chemical and isotope data were used to decipher the impact of fluid availability and transfer behavior, i.e. carbonate-buffered versus diagenetic-fluid buffered, and isotope and element exchange behavior, and analyzed in context to textural alteration features. These data suggest that during diagenesis, the evolution to more sustainable (diagenetically induced) fabrics is accompanied by individual reaction steps traced by elemental and isotopic signatures. Kinetics, and thus degree of diagenetic alteration of biominerals at a given exposure to physicochemical alteration conditions is initially strongly controlled by the micro- to nano-scale internal architecture governing the availability and transfer of aqueous fluids. Results shown here have significance for those concerned with biogenic carbonate archives and have wider implications for a mechanistic understanding of carbonate diagenesis.

Various marine calcifiers form exoskeletons via an amorphous calcium carbonate (ACC) precursor phase and magnesium plays an important role in the temporary stabilization of this metastable phase. Thus, the use of Mg isotope ratios of marine biogenic carbonates as a proxy to reconstruct past seawater chemistry calls for a detailed understanding of the mechanisms controlling Mg isotope signatures during the formation and transformation of ACC to the final crystalline carbonate mineral. For this purpose we have investigated the Mg isotope fractionation between (Ca,Mg)CO 3 solids and aqueous fluids at 25 °C and pH = 8.3 during (i) the direct precipitation of crystalline Mg-calcite and (ii) the formation of Mg-rich ACC (Mg-ACC) and its transformation to Mg-calcite. The outcome documents that the small Mg isotope fractionation between Mg-ACC and reactive fluid ( Δ Mg ACC -fluid 26 = − 1.0 ± 0.1 ‰ ) is not preserved during the transformation of the ACCs into Mg-calcite. Following a pronounced isotopic shift accompanying the transformation of Mg-ACC into Mg-calcite, Δ 26 Mg calcite-fluid progressively decreases with reaction progress from ∼ − 3.0 ‰ to − 3.6 ‰ , reflecting both the approach of isotopic equilibrium and the increase of calcite Mg content (to near 20 mol % Mg). In contrast the crystalline Mg-calcite precipitated directly from the reacting fluid, i.e. lacking a discernable formation of an amorphous precursor, exhibits only small temporal variations in Δ 26 Mg calcite-fluid which overall is affected by the precipitation kinetics. The values found in this study at the onset of Mg-ACC precipitation for Mg isotope fractionation between Mg-ACC and the fluid ( Δ Mg ACC -fluid 26 = − 1.0 ‰ ) and between Mg-ACC and Mg 2+ (aq) ( Δ Mg ACC -Mg 2 + ( aq ) 26 = + 2.0 ‰ ) are consistent with the formation of a hydrated Ca nanoporous solid accommodating Mg bicarbonate/carbonate species in combination with hydrated magnesium. This material crossed by percolating channels filled with the reacting fluid easily converts to Mg-rich calcite via exchange and/or dissolution/precipitation reactions. The results of this study provide new insights on the acquisition of the Mg chemical and isotopic signatures by the skeletal marine carbonates precipitated in confined media from strongly supersaturated fluids. They also offer new guides for the interpretation of the isotopic signature of these organisms for paleo-environmental reconstructions.

The quantification of the sources and sinks of elements to the oceans forms the basis of our understanding of global geochemical cycles and the chemical evolution of the Earth's surface. There is, however, a large imbalance in the current best estimates of the global fluxes to the oceans for many elements. In the case of strontium (Sr), balancing the input from rivers would require a much greater mantle-derived component than is possible from hydrothermal water flux estimates at mid-ocean ridges. Current estimates of riverine fluxes are based entirely on measurements of dissolved metal concentrations, and neglect the impact of riverine particulate dissolution in seawater. Here we present 87Sr/86Sr isotope data from an Icelandic estuary, which demonstrate rapid Sr release from the riverine particulates. We calculate that this Sr release is 1.1–7.5 times greater than the corresponding dissolved riverine flux. If such behaviour is typical of volcanic particulates worldwide, this release could account for 6–45% of the perceived marine Sr budget imbalance, with continued element release over longer timescales further reducing the deficit. Similar release from particulate material will greatly affect the marine budgets of many other elements, changing our understanding of coastal productivity, and anthropogenic effects such as soil erosion and the damming of rivers.