Sedimentary carbonates: fabrics, ultrastructures and geochemistry

Sedimentary calcium and magnesium carbonate minerals have recorded the evolution of life, climate, and CO2 cycling for billions of years through their physical and chemical properties. These largely depend on crystallization pathways related to fluid pH and supersaturation, biological processes, presence of additives and redox conditions. As such, crystallization pathways define the properties of biominerals and abiotic carbonates that are used to reconstruct Earths history. Crystallization pathways, often preserved in carbonate ultrastructures have been widely investigated for biominerals and bio-mediated calcium and Ca-Mg carbonates by using High-resolution Transmission Electron Microscopy (HRTEM). Synchrotron micro-X-ray fluorescence facilitates trace element mapping highlighted heterogeneities in their distribution as related to fabrics. Nano and micro-scale investigations of biominerals and bio-mediated carbonates have revealed that they consist of crystalline, nanocrystalline and amorphous phases, which may co-exist in the same sample and influence the distribution of trace, minor and major elements. Critically, the clustering of nanoparticles is considered a marker of biotic Ca-Mg-carbonates, whereas monomer- by-monomer crystal growth seems to characterize abiotic minerals. However, HRTEM investigation of abiotic sabkha dolomicrite formed primarily by aggregation of nanoparticles as a response to fluctuating aqueous chemistry. Abiotic cave CaCO3 minerals (speleothems), when observed by HRTEM also revealed that nanoparticle attachment is one of several crystallization pathways, that result in inter-and intracrystalline micro to nano-porosity and the formation of intracrystalline defects. Critically, both inter- and intra-crystalline porosity and defects accommodate both organic macromolecules and inorganic colloids. The exploration of non-classical crystallization pathways, exemplified by particle attachment, explains the frequently observed non-equilibrium integration of trace elements. This phenomenon extends to the heterogeneous lateral distribution of both trace elements and organic molecules, providing insights into the intricate processes shaping the crystalline matrix. Nano-scale observations further revealed that porosity follows crystallographic orientations, which leads to a hypothesis that sector zoning is responsible for lateral heterogeneity of organic and inorganic impurities. However, sector zoning largely stems from a classical monomer-by-monomer growth under pH and supersaturation ranges that are commonly lower than what expected for particle attachment. It is then plausible that local pH and supersaturation conditions as well as the presence of impurities result in changes in crystallization pathways. Nanoparticles participating in non-classical particle attachment may consist of amorphous calcium carbonate (ACC), whose uptake of trace elements differs from that of calcite. Transformation of ACC into calcite may ultimately result in an observed non-equilibrium partitioning of trace elements in the final phase. This phenomenon, in addition to the possibility that pores and crystal defects host impurities, suggests that multiple crystallization pathways explain kinetic effects that hinder a direct and constant link from proxy data to environmental parameters in carbonate archives of Earths history. It is proposed that fabrics of abiotic carbonates, their ultrastructure and geochemistry should be granted the same level of investigation given to biominerals when interrogating their capability to accurately record climate (or environmental) change. Examples of how this can be achieved will be presented for case-studies including Triassic dolomicrite, Pleistocene subglacial carbonates from Antarctica and Holocene tropical stalagmites.