M. Ortega-Huertas

Thermal decomposition of calcite: Mechanisms of formation and textural evolution of CaO nanocrystals

Abstract Field emission scanning electron microscopy (FESEM), two-dimensional X-ray diffraction (2DXRD), and transmission electron microscopy coupled with selected area electron diffraction (TEMSAED) analyses of the reactant/product textural relationship show that the thermal decomposition of Iceland spar single crystals according to the reaction CaCO3(s) → CaO(s) + CO2(g) is pseudomorphic and topotactic. This reaction begins with the formation of a mesoporous structure made up of up to four sets of oriented rod-shaped CaO nanocrystals on each rhombohedral cleavage face of the calcite pseudomorph. The four sets formed on (101̅4)calcite display the following topotactic relationships: (1) (12̅10)calcite//(110)CaO; (2) (1̅104)calcite┴ (110)CaO; (3) (1̅018)calcite//(110)CaO; and (4) (01̅14)calcite┴(110)CaO; with [841]calcite//[11̅0]CaO in all four cases. At this stage, the reaction mechanism is independent of PCO2 (i.e., air or high vacuum). Strain accumulation leads to the collapse of the mesoporous structure, resulting in the oriented aggregation of metastable CaO nanocrystals (~5 nm in thickness) that form crystal bundles up to ~1 μm in cross-section. Finally, sintering progresses up to the maximum T reached (1150 °C). Oriented aggregation and sintering (plus associated shrinking) reduce surface area and porosity (from 79.2 to 0.6 m2/g and from 53 to 47%, respectively) by loss of mesopores and growth of micrometer-sized pores. An isoconversional kinetic analysis of non-isothermal thermogravimetric data of the decomposition of calcite in air yields an overall effective activation energy Eα = 176 ± 9 kJ/ mol (for α > 0.2), a value which approaches the equilibrium enthalpy for calcite thermal decomposition (177.8 kJ/mol). The overall good kinetic fit with the F1 model (chemical reaction, first order) is in agreement with a homogeneous transformation. These analytical and kinetic results enable us to propose a novel model for the thermal decomposition of calcite that explains how decarbonation occurs at the atomic scale via a topotactic mechanism, which is independent of the experimental conditions. This new mechanistic model may help reinterpret previous results on the calcite/CaO transformation, having important geological and technological implications.

Evolution of illite/smectite from early diagenesis through incipient metamorphism in sediments of the Basque-Cantabrian Basin

Prograde evolution of illite/smectite occurring in an unusually-thick (8000 m) sequence of Mesozoic-Cenozoic sediments in the Basque-Cantabrian Basin, Spain, has been studied using XRD and TEM/AEM. The sediments, which are only slightly tilted, cover the range from smectite to illite, and the most deeply buried ones are unique in that they span the range from diagenesis through low-grade metamorphism (anchizone), with no apparent overprinting due to tectonic deformation.Pelites are absent from the shallow section, but smectite occurs in marls as high-charge, K-dominant and low-charge, K-poor anastomosing arrays of layers. At intermediate depths, authigenic clay is identified largely as Rl I/S, coexisting with packets of R≫3 I/S (nearly pure illite), where illite-like and smectitelike layers can be identified by contrast in TEM images, which is consistent with XRD data. The authigenic clay of the deepest samples consists of illite with no or almost no expandable layers, which occurred as packets with layers largely subparallel to bedding, K-deficient composition in comparison with muscovite, lMd-like SAED patterns, and 100 A mean packet thickness. There is no evidence of deformation stress-induced, non-bedding-parallel clays in the deepest samples. Detrital micas with either a phengiterich or a phengite-poor composition range dominate the phyllosilicate fraction of all the samples. Detrital micas show no changes over the diagenesis/metamorphism range and appear to have behaved as if isolated from authigenic clays.Authigenic clays occur as bedding-subparallel packets that evolved during passive burial metamorphism through dissolution/crystallization of less-evolved clays. Where illite-like and smectite-like layers can be identified, TEM images imply a discontinuous series in which packets of Rl I/S (50% I) transform to packets of nearly-pure illite, that is, an Ostwald-step-rule-like sequence. Such immature illite remains unmodified with further burial, and is apparently the potential predecessor of stress-induced, highly-evolved mica of higher-grade, tectonically-deformed pelites.

Geochemical evidence for enhanced productivity during S1 sapropel deposition in the eastern Mediterranean

The geochemistry of the youngest Mediterranean sapropel layer suggests changes in productivity and water column oxygen conditions during sapropel deposition. The Ba-enriched interval is broader than the organic-carbon-rich interval of this sapropel. We suggest that the Ba-enriched horizon records the original thickness of the sapropel prior to subsequent partial oxidation. The main carrier of Ba is barite, as microcrystals (0.5–5 µm ) having a morphology characteristic of marine barite, particularly abundant beneath high productivity regions. Ba concentrations do not change at the sapropel layer oxidation front and diagenetic barite crystals are absent, thus the Ba-enriched layer reflects original oceanic conditions of increased biological productivity during sapropel deposition and not diagenetic Ba remobilization. Paleoredox indicators point to restricted oxygenated bottom water but not to fully anoxic conditions. Detrital elements within this layer indicate a lower eolian terrigenous input, enhanced humidity, and increased precipitation/runoff, thus likely higher nutrient supply. Supporting table is available on diskette or via Anonymous FTP from kosmos.agu.org, directory APEND (Username = anonymous, Password = Guest). Diskette may be ordered by mail from AGU, 2000 Florida Ave., N. W., Washington, DC 20009 or by phone at 800-966-2481;

Genesis and evolution of strontium deposits of the granada basin (Southeastern Spain): Evidence of diagenetic replacement of a stromatolite belt

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Stratigraphy and geochemical anomalies of the early Toarcian oxygen-poor interval in the Umbria-Marche Apennines (Italy)

Abstract There are important strontium deposits in the Granada Basin, the most noteable of which (Montevives) has an annual production of approximately 50,000 tons of almost pure celestite. Two types of mineralization can be recognized: a primary variety consisting of stromatolitic carbonate that has been partially replaced by celestite, and a secondary variety consisting of celestite-pebble karst deposits. Both are included in an evaporitic Messinian succession. The primary variety of mineralization is within carbonates that interfinger with, and prograde across, gypsum deposits. The development of these deposits can be interpreted in the context of the general evolution of the Granada Basin during Late Tortonian and Messinian times. Open marine conditions prevailed during the late Tortonian. During the transition from Tortonian to Messinian a restriction of the basin resulted in evaporite sedimentation, with stromatolites thriving at the basins margin. The stromatolites were distributed along a coastal belt that was limited on the east by the tectonically active Sierra Nevada with its local alluvial fans. Runoff from the Sierra Nevada produced a freshwater lens and surface salinities that permitted the development of stromatolites, rather than the accumulation of gypsum. The replacement of stromatolitic carbonate by celestite occurred within the mixing zone of the coastal aquifers during sedimentation and/or early diagenesis. An essentially marine origin is considered for the strontium. Supplementary influxes from continental weathering are also thought to have been produced. Further restriction of the Granada Basin led to complete desiccation and the deposition of a 20 m thick halite layer. Later, gypsum deposits were exposed, and resulting cavities (“dolinas”) were filled with celestite pebbles. The return of sediment accumulation within lakes buried and preserved these deposits.

Change in the chicken eggshell cuticle with hen age and egg freshness

Abstract A multidisciplinary approach is used to demonstrate the occurrence of oxygen-poor sediments in theTenuicostatum Zone (Early Toarcian) within the clayey-marly pelagic sediments of Marne del Monte Serrone Formation (Umbria-Marche basin). This approach involves examination of some geochemical anomalies (trace elements), measurement of Total Organic Carbon and observation of benthic foraminifera and trace fossils. A distinction between “ black shale facies ” (BSF1) and “ black shale-like sediments ” (BSF2) allows better identification of the variable anoxic conditions present within the same basin. A high degree of organic matter preservation and major anoxia extensions occur in the middle-upper part of the Tenuicostatum Zone (Early Toarcian) probably related to maximum flooding-high stand of the global Early Toarcian sea-level rise. Several subenvironments showing pelagic conditions and high primary productivity of planktonic organisms (mainly radiolarians and calcareous nannofossils), have been defined on the basis of organic matter content and positive geochemical anomalies. The diversified physiography of the Umbria-Marche basin, related to synsedimentary tectonic activity and circulation patterns, probably determined different intensities of ventilation conditions on the sea-floor.

K-T boundary spherules from Blake Nose (ODP Leg 171B) as a record of the Chicxulub ejecta deposits

For a fuller understanding of the functionality of the eggshell cuticle, we conducted a detailed study using a wide array of analytical techniques (scanning and transmission microscopy), energy dispersive x-rays, and attenuated total reflection-Fourier transform infrared spectroscopy to analyze the structure, morphology, and chemical composition of this organic coating. This study shows that the cuticle has a compositional gradation with an outer part richer in proteins and an inner part richer in sulfated polysaccharides and phosphates. It also shown that the cuticle composition, thickness, and degree of coverage are highly dependent on hen age and egg freshness. During the course of the first laying year, the thickness and degree of glycosylation of the cuticle decreases with hen age, and at the end of the laying cycle, the cuticle is significantly depleted in lipids. There are also well-defined compositional changes in the cuticle of freshly laid eggs as time passes and there is a notable increase in the permeability of the eggshell after 24 h due to cuticle drying. We discuss how these changes in the cuticle can affect the food safety of eggs in relation to the risk of trans-shell contamination by bacteria (i.e., Salmonellosis).

Review of the mineralogy of the Cretaceous-Tertiary boundary clay: evidence supporting a major extraterrestrial catastrophic event

Abstract The Cretaceous-Tertiary (K-T) boundary interval recovered by the ODP Leg 171 at Site 1049 (Blake Nose, NW Atlantic) contains a thick (9–17 cm) spherule bed marking the boundary. The spherules are mainly perfect spheres with a lesser proportion of oval spherules. They usually range from 100 to 1000 μm. This bed represent the diagenetically altered impact ejecta from Chicxulub and further supports this structure as the site of the K-T impact. Mineralogical and geochemical investigations indicate that impact-generated glass was altered to smectite. Transmission electron microscopy observations revealed in some spherules that smectite is forming from a Si-rich or Ca-rich material, which could suggest a precursor similar to Haitian glasses. The variable thickness and the presence of some Cretaceous planktonic foraminifera and clasts of Cretaceous chalk suggest reworking of the ejecta material. However, the spherule bed confirms that a large volume of the Chicxulub ejecta material reached the Blake Nose Plateau.

Geochemistry of the Cretaceous-Tertiary boundary at Blake Nose (ODP Leg 171B)

Abstract The proposed impact event at the end of the Cretaceous resulted in mass extinctions and subsequently significant variations in the geochemical and mineralogical composition of the sediments marking the K/T boundary. The impact-generated material derived from target rocks produced the ejecta layer deposits around Chicxulub crater, which were subsequently diagenetically altered to mainly smectite in marine sections and to kaolinite in continental sections. The fireball layer represents the cosmic dust dispersed and deposited globally and contains smectite derived from the alteration of microkrystites and the finest fraction. The lowermost Danian clay layer, recognized in marine sections, resulted from the sudden decrease in ocean productivity and represents a reduced sedimentation deposit. Its clay mineral associations depend on local environmental conditions and diagenetic processes. Overall, the diagenetic alteration of the boundary materials resulted in a significant modification of original signatures. The composition of the clay mineral phases can, however, still be evidence of the nature of the precursor materials providing evidence for an extraterrestrial impact event.

Climate, tectonics and meteoritic impact expressed by clay mineral sedimentation across the Cretaceous-Tertiary boundary at Blake Nose, Northwestern Atlantic

Abstract The Cretaceous-Tertiary (K-T) boundary at Blake Nose, in the NW Atlantic, is recorded by a coarse, poorly graded and poorly cemented layer mostly consisting of green spherules that are mainly composed of smectite. Geochemical patterns across the boundary are governed by the source material of the spherule bed and postdepositional processes. The chemical composition and the nature of this bed indicate that it derived from melted target rocks from the Chicxulub impact structure. Ir and other typical extraterrestrial elements do not present significant enrichments, which suggests that the spherule bed material derived from crustal rocks. Ir instead reaches its highest concentration in the burrow-mottled calcareous ooze above the spherule bed, suggesting that it is associated to the finest fraction deposited after the target-rock-derived material. Only the Ni and Co content show slight enrichments within the upper part of the spherule layer, although most of the trace element profiles resulted from diagenetic alteration. During the alteration of glass to smectite, the concentrations of certain trace elements, such as the rare earth elements, were severely changed. In addition, oxygen-poor conditions also led to the remobilization of redox-sensitive elements, which show enhanced concentration at the top or above the spherule bed. Diagenetic remobilization may have also affected the Ir concentration.