ALBERT

Description: Persistent anoxia and the lack of a skeletal silica sink through the Precambrian would have promoted a variety of reactions between iron and dissolved silica through much of Earth’s early history. However, although both iron and silica have each left clear fingerprints in the Precambrian record, evidence for their interaction, and the attendant biogeochemical consequences, is cryptic. Here, experimental evidence is presented showing that Fe 2+ and SiO 2 (aq) in anoxic seawater–derived solutions promote rapid nucleation of a hydrous Fe(II)-silicate gel at 25 °C. By merging experimental data with crystallographic constraints, we observe that structural rearrangement and dehydration produce Fe-rich serpentine nanoparticles within the gel, which eventally aggregate to form the mineral greenalite. This nonclassical crystal growth pathway is consistent with the crystal structure of greenalite and with its syndepositional origin in iron formation. A mechanistic underpinning for greenalite precipitation also permits new constraints on the chemistry of ferruginous Precambrian waters. For example, greenalite may have nucleated from waters with a pH as high as 7.7–8.3, implicating alkalinity as a key trigger in coupling and decoupling Fe and Si during the anoxic deposition of several late Archean and Paleoproterozoic iron formations. The common, though not exclusive, association of greenalite with deeper-water iron formation facies (i.e., below the fair-weather wave base) suggests that the upwelling of silica-rich alkaline water masses played an important role in driving precipitation. More broadly, our results prompt a reconsideration of the inorganic reactions that determine the upper limits on water-column Fe 2+ concentrations in nonsulfidic seawater. The primary precipitation of greenalite and/or siderite would set a ceiling for dissolved Fe 2+ that is sensitive to pH, and higher than previously estimated. These results indicate that a better understanding of greenalite distributions in chemical and siliciclastic sediments will help to disentangle the coevolution of redox and acid-base chemistries through the Precambrian.

Description: The lacustrine carbonate reservoirs of the South Atlantic host significant accumulations of chemically reactive and Al-free Mg-silicate minerals (e.g. stevensite, kerolite and talc). Petrographic data from units such as the Cretaceous Barra Velha Formation in the Santos Basin suggest that Mg-silicate minerals strongly influenced, and perhaps created, much of the observed secondary porosity. The diagenetic interactions between reactive Mg-silicate minerals and carbonate sediments are, however, poorly known. Here we develop a conceptual model for the origin of secondary porosity in the Barra Velha Formation guided by considerations of the chemistry that triggers Mg-silicate crystallization, as well as the geochemical and mineralogical factors that act as prerequisites for rapid Mg-silicate dissolution during early and late diagenesis. We conclude that sub-littoral zones of volcanically influenced rift lakes would have acted as the locus for widespread Mg-silicate accumulation and preservation. Organic-rich profundal sediments, however, would be especially prone to Mg-silicate dissolution and secondary porosity development. Here, organic matter diagenesis (especially methanogenesis) plays a major role in modifying the dissolved inorganic carbon budget and the pH of sediment porewaters, which preferentially destabilizes and then dissolves Mg-silicates. Together, the sedimentological, stratigraphic and geochemical predictions of the model explain many enigmatic features of the Barra Velha Formation, providing a novel framework for understanding how Mg-silicate–carbonate interactions might generate secondary porosity more broadly in other lacustrine carbonate reservoirs across the South Atlantic.

Description: Biomineralization marks one of the most significant evolutionary milestones among the Eukarya, but its roots in the fossil record remain obscure. We report crystallographic and geochemical evidence for controlled eukaryotic biomineralization in Neoproterozoic scale microfossils from the Fifteenmile Group of Yukon, Canada. High-resolution transmission electron microscopy reveals that the microfossils are constructed of a hierarchically organized interwoven network of fibrous hydroxyapatite crystals each elongated along the [001] direction, indicating biological control over microstructural crystallization. New Re-Os geochronological data from organic-rich shale directly below the fossil-bearing limestone constrain their age to 〈810.7 ± 6.3 million years ago. Mineralogical and geochemical variations from these sedimentary rocks indicate that dynamic global marine redox conditions, enhanced by local restriction, may have led to an increase in dissolved phosphate in pore and bottom waters of the Fifteenmile basin and facilitated the necessary geochemical conditions for the advent of calcium phosphate biomineralization.

Description: Mg-silicate minerals (e.g., stevensite, kerolite, talc, sepiolite) play an important role in the construction of facies models in lacustrine and peri-marine environments because they are sensitive to changes in solution chemistry. However, the response of Mg-silicate mineralogy to changing aqueous chemistry is only broadly understood because the mechanisms underpinning the co-precipitation of Mg 2+ and SiO 2 (aq) from surface water, and subsequent Mg-silicate crystallization, are unclear. Here we describe the results of experiments designed to systematically examine the effects of pH, Mg/Si and salinity of the parent solution on the nature of initially precipitated products. Structural interrogation of the products with X-ray diffraction (XRD), Fourier-transform infrared spectroscopy (FTIR) and thermal analysis (TGA/DTA) allow comparison of synthetic products with naturally occurring crystalline counterparts. In general, Mg 2+ and SiO 2 (aq) co-precipitation and nucleation of Mg-silicate layer structures first involves the rapid formation of 2:1 layers with trioctahedral occupancy and a mean coherent X-ray scattering domain between 1–2 unit cells with respect to the c axis. Well defined but diffuse hk reflections indicate two-dimensional growth, turbostratic stacking and highly variable interlayer hydration. Diffuse reflectance FTIR shows numerous structural similarities with stevensite, kerolite and sepiolite. However, TGA/DTA analysis indicates the presence of variable kerolite/stevensite interstratification not readily detectable through XRD analyses, as well as a significant degree of surface and interlayer hydration (e.g. 15–20 wt.%). We observe a number of clear trends in the products with respect to solution chemistry. For example, at low salinity, kerolite-like products dominate at high Mg/Si and high pH, whereas sepiolite-like products are formed at lower pH and lower Mg/Si. At high salinity and high Mg/Si, stevensite-like products are favoured at high pH and kerolite-like products dominate at lower pH, whereas a decrease in Mg/Si of the solution leads to sepiolite-like products at low pH and only stevensite-like products at high pH. Higher pH leads to an increase in octahedral vacancies which favour stevensite-like products; this may result from a higher rate of two-dimensional tetrahedral sheet expansion relative to the octahedral sheet, as inferred from studies of silica oligomerization and brucite growth kinetics. Together, our results indicate that the neoformation of Mg-rich silicates from solution may often begin with the rapid nucleation of hydrated 2:1 layers. Subsequent dehydration leads to progressive layer stacking order and could occur in response to wetting/drying cycles, prolonged exposure to high salinity solutions, or burial and heating. The surface and interlayer water associated with these products is undoubtedly an important source of diagenetic water in Mg-silicate-bearing successions, and the chemistry of this water upon later diagenesis should be a focus of future investigation.

Description: The idea is tested that the evolution of the Chalk’s clay mineral assemblage during diagenesis can be deduced by examining the relationships between its clay mineralogy, particle size distribution pattern, and the timing and trace element chemistry of the calcite cement. The preliminary results from five different examples of cementation developed at different stages of diagenesis in chalks with smectite-dominated clay assemblages suggest that this is a promising line of investigation. Soft chalks with minor amount of anoxic series calcite cement poor in Mg, Fe and Mn are associated with neoformed trioctahedral smectite and/or dioctahedral nontronite and talc. Hard ground chalk with extensive anoxic series calcite cement enriched in Mg and relatively high Fe, Mn and Sr are associated with neoformed glauconite sensu lato , berthierine and dioctahedral smectite, possibly enriched in Fe. The chalk associated with large ammonites shows extensive suboxic series calcite cement enriched in Mg, Mn and Fe that show no obvious correlation with its clay mineralogy. Nodular chalks with patchy suboxic series calcite cement enriched in Fe are associated with neoformed dioctahedral smectite, possibly enriched in Al, and berthierine. Regionally hardened chalk with extensive suboxic calcite cement and relatively high trace element contents contain pressure dissolution seams enriched in kaolin and berthierine. Laser-based particle-size distribution patterns suggest that each type of lithification has a typical complex clay mineral population, indicating that subtleties in mineralogy are not being identified and that there could be some control on the size and shape of the clay crystals by the different types of cementation.