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Formation and Evolution of Glauconite. New Scale Approach
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Formation and Evolution of Glauconite. New Scale Approach

A special issue of Minerals (ISSN 2075-163X). This special issue belongs to the section "Environmental Mineralogy and Biogeochemistry".

Deadline for manuscript submissions: closed (17 February 2023) | Viewed by 18195

Special Issue Editor

Prof. Dr. Pierre Giresse

E-Mail Website
Guest Editor
Centre of Education and Research on Mediterranean Environments (CEFREM), UMR CNRS 5110, Perpignan Via Domitia University, 66860 Perpignan, France
Interests: glauconites; phosphates; tropical environments (oceans and lakes); African Quaternary environments

Special Issue Information

Dear Colleagues,

For a long period of time, particular attention was paid to glauconitisation in unburied sediments lying on the continental shelves of present oceans. The processes observed and analyzed may have served as models for studies of glauconite in neritic zones of Cenozoic or even Mesozoic basins. Access to the sedimentary domains of the deep oceans, particularly those of contouritic accumulation, has made it possible to discover new aspects of glauconitization. Thus, the prevailing control by fairly high temperature water has become obsolete, and the influence of the nature of continental flows has become differently analysed.

Sediments from contouritic accumulation provide a condensed and undisturbed sedimentary record without long periods of sediment erosion. Glauconitic grains could possibly integrate the signature of bottom water masses over prolonged periods of time, which, while preventing their use in high-resolution studies, would provide an effective means for yielding reliable average estimates on past εNd  signatures of bottom water masses. Glauconitic grains are probably best suited for paleoceanographic reconstructions than foraminifera and leached Fe-oxyhydroxide fractions, which appear to be influenced by sediment redistribution and the presence of terrestrial continental Fe-oxides, respectively.

Direct access to the compositions of the micromilieux of neoformation has largely renewed information, chemical or crystallographic, limited for a long period of time to macromesures. Various granular supports (mudclasts, faecal pellets, and foraminifera infillings) include inherited 1:1 interstratified clays (or Te-Oc; i.e., clay minerals consisting of one tetrahedral sheet and one octahedral sheet, such as kaolinite) that become gradually replaced by 2:1 clays (Te-Oc-Te) dominated first by smectite and then by glauconite. Recent studies have shown that, in small pores, part of the water is attached to the wall, and the water’s activity is diminished; the precipitation of a great number of mineral species is thereby made easier, and their stability domains are changed.

Specific methodological approaches permit studying the mineralogy and chemistry of fine-scale mineral phases and avoids the global aspect of analytical methods that are generally used in previous studies. Wide field micrographs taken at a mean direct magnification of 100.000 show the intimate and characteristic organizations of the main phases that occur in a single grain. One or several "fine" (about 10 nanometers scale) microchemical analyses could be recorded, directly coupled with each interesting and well-identified structure image observed in HRTEM.

Prof. Dr. Pierre Giresse
Guest Editor

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Keywords

  • glauconitisation
  • water-sediment interface
  • microenvironment
  • nanostructures
  • neoformed minerals
  • neodymium isotopes

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Published Papers (6 papers)

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Research

23 pages, 11364 KiB  
Article
The Behavior of Rare Earth Elements during Green Clay Authigenesis on the Congo Continental Shelf
by Germain Bayon, Pierre Giresse, Hongjin Chen, Marie-Laure Rouget, Bleuenn Gueguen, Gabriel Ribeiro Moizinho, Jean-Alix Barrat and Daniel Beaufort
Minerals 2023, 13(8), 1081; https://doi.org/10.3390/min13081081 - 14 Aug 2023
Cited by 5 | Viewed by 1835
Abstract
Clay mineral authigenesis at continental margins plays an important role in global marine element cycles. However, despite being increasingly used as tracers for both modern and past oceanographic conditions, the behavior of the rare earth elements (REEs) and their isotopes during marine clay [...] Read more.
Clay mineral authigenesis at continental margins plays an important role in global marine element cycles. However, despite being increasingly used as tracers for both modern and past oceanographic conditions, the behavior of the rare earth elements (REEs) and their isotopes during marine clay authigenesis still remains poorly known. In this study, we report on a detailed geochemical investigation of glauconite from the West African continental shelf, near the mouth of the Congo River. Elemental, neodymium, and hafnium isotope analyses were conducted on both acid leachate and separated clay-size fractions of glauconite pellets, in order to investigate the behavior of REE during the formation of authigenic clays. Our data indicate that kaolinite dissolution and subsequent Fe-bearing clay authigenesis act as a net source of REEs to seawater. We show that enhanced glauconitization, as inferred from increasing Fe and K contents, is accompanied by significant decoupling of the REE toward markedly LREE-enriched shale-normalized patterns in neoformed clay separates. Using both Nd and Hf isotopes and SEM observations, we rule out any seawater influence and argue that this shift primarily reflects the progressively overwhelming presence of insoluble nanocrystals of detrital LREE-rich phosphates, which are known to occur in close association with kaolinite in tropical soils. Due to their marked insolubility in surface environments, such nanocrystals can be preserved during kaolinite dissolution and subsequently incorporated into the aggregates of authigenic green clays forming the peloids. Most strikingly, we show that the combined influence of net REE loss (due to kaolinite dissolution) and decoupling (due to subsequent entrapment of inherited LREE-bearing accessory phases into neoformed clay minerals) is accompanied by preferential release of a dissolved REE fraction characterized by seawater-like distribution patterns. These findings reinforce the emerging view that clay mineral dissolution and authigenesis at continental margins possibly play a major role in marine REE cycling. Full article
(This article belongs to the Special Issue Formation and Evolution of Glauconite. New Scale Approach)
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14 pages, 3269 KiB  
Article
Synchrotron Microanalytical Characterization and K/Ar Dating of the GL-O-1 Glauconite Reference Material at the Single Pellet Scale and Reassessment of the Age of Visually Mature Pellets
by Sidney R. Hemming, Tanzhuo Liu, Paul Northrup, Sarah Nicholas, E. Troy Rasbury, Heng Chen, Alice Warden, Amanda Chen, Ruipeng Li, Ryan Tappero, Stephen E. Cox, Jenna Everard, Silu Wang, Michael Deluca, Benjamin Bostick and Alexander N. Halliday
Minerals 2023, 13(6), 773; https://doi.org/10.3390/min13060773 - 5 Jun 2023
Cited by 3 | Viewed by 1959
Abstract
The K/Ar chronology of glauconite pellets is a long-used method for directly dating marine sedimentary deposits. Many papers have explored the processes that form glauconite and the factors that lead to greater reliability in the ages. Although K/Ar ages of glauconite are generally [...] Read more.
The K/Ar chronology of glauconite pellets is a long-used method for directly dating marine sedimentary deposits. Many papers have explored the processes that form glauconite and the factors that lead to greater reliability in the ages. Although K/Ar ages of glauconite are generally in agreement with other measures of stratigraphic age, there are examples of occurrences with ages too old and examples with ages too young. This paper seeks to build on the accumulated knowledge of glauconite, using synchrotron radiation to non-destructively characterize individual pellets and then consecutively measure the argon and potassium to obtain a K/Ar age. This strategy provides the advantage of measurements on a single aliquot while avoiding recoil loss of 40Ar in the nuclear reactor during irradiation for 40Ar/39Ar dating. We have used the glauconite reference material GL-O-1 to showcase several non-destructive methods for evaluating the maturity of individual pellets. In our argon measurements, we have found that the radiogenic argon concentration of large bulk samples underestimates the values for individual visually mature pellets, and we determined a K/Ar age of 101.0 ± 0.3 Ma (1σ SEM), M.S.W.D. 0.54 from 15 of 16 visually mature individual pellets. This age is 6% older than the reference value of 95.03 ± 1.11 Ma (1σ), and it is in good agreement with constraints from the U-Pb dating of volcanic minerals near the Albian–Cenomanian boundary. Full article
(This article belongs to the Special Issue Formation and Evolution of Glauconite. New Scale Approach)
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20 pages, 23783 KiB  
Article
Authigenic Fe Mineralization in Shallow to Marginal Marine Environments: A Case Study from the Late Paleocene—Early Eocene Cambay Shale Formation
by Tathagata Roy Choudhury, Pragya Singh, Arpita Chakraborty and Santanu Banerjee
Minerals 2023, 13(5), 646; https://doi.org/10.3390/min13050646 - 7 May 2023
Cited by 2 | Viewed by 1990
Abstract
The late Paleocene–early Eocene warm greenhouse conditions, characterized by elevated pCO2 levels in the atmosphere and a dramatic increase in sea surface temperature, prompted abundant authigenic glauconite formation within the shallow marine sediments worldwide by lowering the net sedimentation rate, increasing organic [...] Read more.
The late Paleocene–early Eocene warm greenhouse conditions, characterized by elevated pCO2 levels in the atmosphere and a dramatic increase in sea surface temperature, prompted abundant authigenic glauconite formation within the shallow marine sediments worldwide by lowering the net sedimentation rate, increasing organic productivity and expanding the oxygen minimum zones to shallow oceans. The early Eocene marginal marine Cambay Shale Formation experienced episodes of marine inundation represented by limestone–green shale alternations. The shales host abundant authigenic light-green, dark-green, and brown pellets. A detailed characterization of the pellets of the Valia and Vastan lignite mines, integrating the sedimentological, petrographical, mineralogical, and mineral geochemical data, suggests two distinct varieties of Fe–silicate formation, viz. glauconite and chamosite. While the glauconitic green pellets are ubiquitous to Valia and Vastan mines, brown chamosite pellets are confined within the basal part of the green shale facies alternating with fossiliferous limestone in the Vastan mine. The glauconites of the Valia mine manifest a ‘nascent’ to ‘slightly evolved’ maturation stage of glauconitization, whereas the glauconites of the Vastan mine represent the ‘evolved’ type. The limestone–green shale alternation in the Valia mine is overlain by a ~4 m-thick spherulitic mudstone facies comprising monomineralic sideritic spherulites, reflecting a pure FeCO3 composition. The glauconites in the Cambay Shale Formation transformed from kaolinite-rich clay pellets under dys-oxic depositional conditions. The increasing anoxicity within the microenvironment, possibly amplified by the rapid oxidation of continent-derived organic matter, facilitated chamosite formation instead of glauconite. The increased freshwater influx into the marginal marine depositional environment resulted in immature, K-poor glauconites of the Valia mine. The formation of siderite spherulites overlying the limestone–green shale alternation relates to the beginning of the regressive phase of sedimentation. Full article
(This article belongs to the Special Issue Formation and Evolution of Glauconite. New Scale Approach)
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21 pages, 10837 KiB  
Article
Holocene Glaucony from the Guadiana Shelf, Northern Gulf of Cadiz (SW Iberia): New Genetic Insights in a Sequence Stratigraphy Context
by Adrián López-Quirós, Francisco José Lobo, Isabel Mendes and Fernando Nieto
Minerals 2023, 13(2), 177; https://doi.org/10.3390/min13020177 - 26 Jan 2023
Cited by 4 | Viewed by 2360
Abstract
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 [...] Read more.
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. Full article
(This article belongs to the Special Issue Formation and Evolution of Glauconite. New Scale Approach)
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27 pages, 4870 KiB  
Article
Quaternary Glauconitization on Gulf of Guinea, Glauconite Factory: Overview of and New Data on Tropical Atlantic Continental Shelves and Deep Slopes
by Pierre Giresse
Minerals 2022, 12(7), 908; https://doi.org/10.3390/min12070908 - 20 Jul 2022
Cited by 10 | Viewed by 3112
Abstract
For a long time, particular attention was paid to glauconitization in the surficial sediments lying on the outer continental shelves of present oceans. Subsequently, the processes observed and analyzed may have served as models for studies of glauconite in Cenozoic or even Mesozoic [...] Read more.
For a long time, particular attention was paid to glauconitization in the surficial sediments lying on the outer continental shelves of present oceans. Subsequently, the processes observed and analyzed may have served as models for studies of glauconite in Cenozoic or even Mesozoic shelf deposits. Access to the sedimentary domains of deep oceans, particularly those of contouritic accumulation fields, has made it possible to discover unexpected processes of glauconitization. Thus, the long-term prevalence of control using fairly high-temperature water has become obsolete, and the prerequisite influence of continental flows has come to be considered on a new scale. Frequently, sediments from contouritic accumulation provide a condensed and undisturbed sedimentary record without periods of sediment erosion. Glauconitic grains could possibly integrate the signatures of bottom-water masses over prolonged periods of time, which, while preventing their use in high-resolution studies, would provide an effective means of yielding reliable average estimates on past εNd signatures of bottom-water masses. In this regard, glauconitic grains are probably better-suited to paleoceanographic reconstructions than foraminifera and leached Fe-oxyhydroxide fractions, which appear to be influenced by sediment redistribution and the presence of terrestrial continental Fe-oxides, respectively. Direct methodological access to the compositions of the semi-confined microenvironments of neoformation has largely renewed the information, chemical or crystallographic, that was previously, and for a long time, restricted to macromeasurements. The various granular supports (mudclasts, fecal pellets, and foraminifera infillings) include inherited 1:1 clays (or Te-Oc; i.e., clay minerals consisting of one tetrahedral sheet and one octahedral sheet, such as kaolinite) that are gradually replaced by 2:1 clays (Te-Oc-Te) dominated first by smectite, and then by glauconite. In small pores, the water’s activity is diminished; as a consequence, the precipitation of a great number of mineral species is thereby made easier, and their stability domains are changed. A specific methodological approach allows the study of the mineralogy and chemistry of the fine-scale mineral phases and to avoid the global aspect of the analytical methods previously used in the initial studies. Wide-field micrographs taken at a mean direct magnification of 100.000 show the intimate and characteristic organization of the main phases that occur in a single grain. One or several “fine” (about 10 nanometers in scale) microchemical analyses can be recorded, and directly coupled with each interesting and well-identified structure image observed in HRTEM. Full article
(This article belongs to the Special Issue Formation and Evolution of Glauconite. New Scale Approach)
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19 pages, 25672 KiB  
Article
Revisiting Glauconite Geochronology: Lessons Learned from In Situ Radiometric Dating of a Glauconite-Rich Cretaceous Shelfal Sequence
by Esther Scheiblhofer, Ulrike Moser, Stefan Lӧhr, Markus Wilmsen, Juraj Farkaš, Daniela Gallhofer, Alice Matsdotter Bäckström, Thomas Zack and Andre Baldermann
Minerals 2022, 12(7), 818; https://doi.org/10.3390/min12070818 - 27 Jun 2022
Cited by 18 | Viewed by 4433
Abstract
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 [...] Read more.
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. Full article
(This article belongs to the Special Issue Formation and Evolution of Glauconite. New Scale Approach)
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