Conditions and mechanism for the formation of iron-rich Montmorillonite in deep sea sediments (Costa Rica margin): Coupling high resolution mineralogical characterization and geochemical modeling

International audienceIron-rich smectite is commonly described in the diagenetic fraction of deep-sea sediment, as millimeter to centimeter aggregates dispersed in the sediment, or as a coating on sedimentary particles or nodules. This study examines several factors to elucidate formation mechanisms of a particular iron-rich smectite and its potential transformation to glauconite. The study combines a detailed mineralogical investigation on natural samples and a chemical modeling approach to assess mineralogical reactions and pathways. Transmission electron microscopy (TEM) observations and analytical electron microscopy (TEM-AEM) analyses were conducted on microtomed samples of millimeter- to centimeter-long green grains. These grains are widespread in pelagic calcareous sediment from the Costa Rica margin. They are composed of pyrites that are partially dissolved and are surrounded by amorphous or very poorly crystallized iron-rich particles. Iron-rich montmorillonite grows from an amorphous precursor and its formation requires the input of Si, O, Mg, K, Na and Ca; our results suggest that these inputs are supported by the dissolution of sedimentary phases such as volcanic glasses, siliceous fossils and silicates. Thermodynamic modeling of fluid-sediment interactions was conducted with the geochemical computer code PhreeqC, using mineralogical and pore fluid compositions from sediment samples and calculated estimates for thermodynamic constants of smectites that are not maintained by the computer code. Simulations confirm the possibility that the green grains are the product of pyrite alteration by seawater under oxidizing conditions. The extent of smectite production is controlled by the kinetics of pyrite dissolution and fluid migration. The absence of aluminum in the Costa Rica margin system explains the formation of an iron-rich montmorillonite instead of glauconite, whereas the presence of calcite that buffers the system explains the formation of an iron-rich montmorillonite instead of iron oxides

Holocene glaucony from the Guadiana shelf, Northern Gulf of Cadiz (SW Iberia): New genetic insights in a sequence stratigraphy context

Glaucony occurrences have been reported both from exposed transgressive and overlying highstand system tracts. However, its occurrences within highstand deposits are often invoked as the result of underlying condensed section reworking. Detailed textural, mineralogical and geochemical reports of glaucony grains in highstand deposits remain elusive. The northern Gulf of Cadiz shelf (SW Iberia) offers a unique opportunity to investigate late Holocene glaucony authigenesis in a well-documented time-stratigraphic context, where transgressive deposits are locally exposed on the seafloor and are laterally draped by highstand muddy deposits. In this study, glaucony grains extracted from a core retrieved from a highstand muddy depocenter off the Guadiana River were investigated by means of digital microscopy, X-ray diffraction (XRD), and electron microscopic methods (FESEM-EDX and TEM-HRTEM). To better constrain the glaucony origin (autochthonous vs. allochthonous) in highstand muddy deposits, glaucony grains from surficial samples—taken from exposed transgressive deposits—were also investigated. Glauconitization in the studied core can be largely attributed to the replacement of faecal pellets from c. ~4.2–1.0 cal. ka BP. Both XRD and TEM-HRTEM analyses indicate that glaucony consists mainly of an R1, with a minor presence of R0, smectite-rich (nontronite) glauconite-smectite mixed-layer silicate, made up of 35–75% glauconitic layers and 65–25% of interstratified smectite layers. At the mineral lattice level, minor individual 7Å layers (berthierine) were also identified by HRTEM. Shallow radial cracks at the pellet surface, along with globular and vermiform-like biomorphic to low packing density lamellar-flaky nanostructures, mineralogical properties, and K-poor content (average 0.4 atoms p.f.u.) indicate a scarcely mature glauconitization process, attesting to formation of the grains in situ (autochthonous). Glaucony grains from exposed transgressive deposits, i.e., in the tests of calcareous benthic foraminifera, do not share a genetic relationship with the grains investigated in the highstand deposits, thus supporting the autochthonous origin of glaucony within the highstand deposits. Our combined dataset provides evidence of a multiphase history for autochthonous glaucony formation in the Guadiana shelf, as its genesis is traced to both transgressive and highstand conditions. While eustatic sea-level changes favoured glaucony formation under transgressive conditions, factors such as protracted low sediment supply and the establishment of a strong nutrient-rich upwelling system in the study area promoted glaucony development during late Holocene highstand conditions.info:eu-repo/semantics/publishedVersio

Mineralogical and Crystal-Chemical Constraints on the Glauconite-Forming Process in Neogene Sediments of the Lower Guadalquivir Basin (SW Spain)

Glaucony is a significant green marine facies in the northwestern passive margin of the Guadalquivir Basin (Spain), where glauconite formed authigenically on a sediment-starved continental shelf, with fecal pellets and benthic foraminiferal tests being the main glauconitized substrates. Results from a study using XRD, TGA-DSC, SEM-EDS, and EPMA have revealed that glauconite is remarkably heterogeneous in mineral composition and chemical maturity, even in a single grain, reflecting a complex interaction of micro-environmental factors, substrate influences and post-depositional alterations. In its early stage, the glauconitization process is consistent with the slow precipitation of a Fe-rich smectite phase, most likely intergrade between nontronite and Fe-montmorillonite end-members, which evolved to a regularly interstratified glauconite-smectite (Gl/S). The Fe-smectite-to-Gl/S transformation is interpreted as a diffusion-controlled reaction, involving sufficient Fe availability in pore water and the constant diffusive transport of seawater K + and Mg2+ ions towards the substrate. The pelletal glauconite is actually a highly evolved Gl/S consisting almost totally of mica layers, with 0.74 ± 0.05 apfu of K+ in the interlayer, while the Gl/S occurring as replacements of foraminiferal tests contains a mean of 7% of expandable layers in the walls and 16% in the chamber fillings, due to rate-limited ion diffusion.We thank Fernando Muñiz (University of Seville) for its collaboration during fieldwork, Josep Tosquella (University of Huelva) for helping with microfossil identification, and Jesús Díaz (University of Huelva) for assistance with thermal analysis. The authors greatly appreciate the quick and valuable review of the manuscript by three anonymous referees

Glaucony from the condensed Lower-Middle Jurassic deposits of the Križna Unit, Western Tatra Mountains, Poland

Lower-Middle Jurassic glaucony-bearing deposits crop out in the Polish part of the Križna Unit in the Western Tatra Mts. These deposits, up to 20 cm thick, consist of glaucony-rich marls and limestones. The glaucony grains constitute up to 30% volume of the deposits. They represent an evolved stage of glauconitization since they contain more than 7% K2O. The content of Al2O3 is high (up to 19.97%, average 16.98%) while the content of Fe2O3 is low (not more than 23.48%, average 12.84%). These features are interpreted as a product of diagenetic processes. The glaucony-bearing deposits were formed at an upper bathyal depth and their rate of deposition was very low, what allowed long-lasting evolution of the glaucony grains. The K-Ar age of the glaucony grains is much younger than the biostratigraphic age of the studied section. The lowering of the K-Ar dates is interpreted as a result of loss of radiogenic Ar from the lattice of the glaucony

Revisiting Glauconite Geochronology: Lessons Learned from In Situ Radiometric Dating of a Glauconite-Rich Cretaceous Shelfal Sequence

The scarcity of well-preserved and directly dateable sedimentary sequences is a major impediment to inferring the Earth’s paleo-environmental evolution. The authigenic mineral glauconite can potentially provide absolute stratigraphic ages for sedimentary sequences and constraints on paleo-depositional conditions. This requires improved approaches for measuring and interpreting glauconite formation ages. Here, glauconite from a Cretaceous shelfal sequence (Langenstein, northern Germany) was characterized using petrographical, geochemical (EMP), andmineralogical (XRD) screening methods before in situ Rb-Sr dating via LA-ICP-MS/MS. The obtained glauconite ages (~101 to 97 Ma) partly overlap with the depositional age of the Langenstein sequence (±3 Ma), but without the expected stratigraphic age progression, which we attribute to detrital and diagenetic illitic phase impurities inside the glauconites. Using a novel age deconvolution approach, which combines the new Rb-Sr dataset with published K-Ar ages, we recalculate the glauconite bulk ages to obtain stratigraphically significant ‘pure’ glauconite ages (~100 to 96 Ma). Thus, our results show that pristine ages can be preserved in mineralogically complex glauconite grains even under burial diagenetic conditions (T < 65 ◦C; <1500 m depth), confirming that glauconite could be a suitable archive for paleo-environmental reconstructions and direct sediment dating.Esther Scheiblhofer, Ulrike Moser, Stefan Löhr, Markus Wilmsen, Juraj Farkaš, Daniela Gallhofer, Alice Matsdotter Bäckström, Thomas Zack, and Andre Balderman

Mineralogical and geochemical characterisation of warm water, shallow marine glaucony from the Tertiary of the London Basin

Glaucony is present in the Palaeocene sediments of the London Basin, from the Thanet Sand Formation to the gravel beds at the base of the Lower Mottled Beds of the Reading Formation. The Upnor Formation glaucony is a rare example of formation in warm, shallow brackish water and this, combined with the ready availability of fresh material from boreholes, make this study important in developing our understanding of this mineral. Glaucony comprises up to 50% of the Upnor Formation, a grey to green sandstone, of variable thickness and composition, that was deposited in a warm, shallow marine to estuarine environment, ~55.6-56.2 Ma. Using morphological criteria, X-ray diffraction data and K+ abundance, the Upnor glaucony may be defined as evolved. The underlying shallow marine Thanet Sand contains <5% of nascent to slightly evolved glaucony. The REE data for the Upnor Formation suggest more than one source for the sediment from which the Upnor glaucony formed, while the Thanet REE data are consistent with a high detrital clay component. In the Upnor Formation, the high proportion of glaucony that occurs as granule fragments rather than whole granules, and the high energy estuarine to shallow marine environment of deposition, are indicative of reworking. The Upnor glaucony is inferred to be intraformationally reworked, rather than derived from the Thanet Sand Formation. The glaucony may have formed in sediments deposited away from the main estuarine channel, and been subsequently reworked into higher energy sediments. Warm seas with freshwater mixing are more typically characteristic of verdine formation than of glaucony. The shallow, brackish environment of deposition suggests that there is not a clear distinction between the environmental requirements of verdine (or odinite) and glaucony (or glauconite), as is often proposed. The highly fractured, delicate nature of some granules indicates that they have experienced some maturation in situ, after reworking. The oxygen and hydrogen isotopic compositions of Upnor Formation shark teeth and glaucony point to formation in low salinity water at ~23±3°C, also consistent with formation in the Upnor Formation, rather than in a fully marine sediment and subsequent reworking. A higher than normal temperature of formation may have increased the rate of evolution of glaucony. Our multidisciplinary study considers many of the factors relating to depositional environment that must be considered when glaucony rich facies are encountered in comparable palaeoenvironmental settings elsewhere in the geological record

Fate of swelling clay minerals during early diagenesis : a case study from Gdańsk Bay (Baltic Sea)

The aim of the study was to recognize the early diagenetic transformations of clay minerals likely taking place in the brackish environment of Gdańsk Bay (Baltic Sea). The Vistula River loads and sediments of the Vistula delta front and prodelta were studied. The mineral compositions of the clay fractions were determined by X-ray diffractometry. The average layer charge (LC) of the expandable interlayers was determined using the O-D vibrational spectroscopy method. The major element content of the studied clays was determined by inductively coupled plasma optical emission spectrometry. The &lt;0.2 μm clay fraction, separated from the river sediments, contained illite-smectite mixed layered minerals, rich in high-charge, dioctahedral smectite (Ilt-Sme), illite, and kaolinite. The same clay fraction, separated from the delta-front sediments, was also composed mainly of Ilt-Sme, illite, kaolinite, and hydroxy-interlayered minerals. The &lt;0.2 μm clay fraction from the prodelta sediments was depleted in Ilt-Sme and enriched in illite and chlorite, relative to the clays from both the river and the delta-front sediments. The LCs (0.45 to 0.56 per formula unit) were higher for clays from the river and the delta front sediments, relative to the clays from the prodelta. The &lt;0.2 μm clay fractions from the prodelta sediments were enriched in MgO, Fe2O3, and K2O, relative to the fine clay fraction from the river. The results indicated that the smectite component of Ilt-Sme, deposited by the Vistula in Gdańsk Bay, underwent chloritization and likely illitization. The chloritization most likely proceeded via formation of hydroxy-interlayers within the smectite. Illite-like minerals, formed at the expense of the smectite with high LC, due to selective adsorption and fixation of K+ from seawater