Micro-XANES mapping of sulphur and its association with magnesium and phosphorus in the shell of the brachiopod, Terebratulina retusa

Biominerals are natural composite materials comprising organic and inorganic components. Detailed knowledge of the nature and distribution of both components is a crucial requirement in order to advance our understanding of biomineral formation, their material properties and preservation potential as well as the interpretation of environmental data. Detailed chemical data are essential for our understanding of the nature and distribution of such components. Micro-XANES mapping at the sulphur K-edge reveals that, in the brachiopod Terebratulina retusa, the sulphate concentration is higher in the outer (primary) layer than in the calcite fibres of the secondary layer. This is co-incident with a higher magnesium concentration. In contrast, the sheaths surrounding the calcite fibres contain sulphur as thiol, confirming the presence of protein while, the sulphur within the fibres themselves, occurs as sulphate. Micro-XANES analysis of the insoluble organic extract from T. retusa indicates the presence of organic sulphate while Micro-Raman spectroscopy confirms that structurally substituted sulphate (SSS) is also present although semi-quantitative Raman spectroscopy carried out in this spectral region (wavenumbers 900–1200) indicates that the sulphate present is at the threshold of detection by Raman spectroscopy. The distribution of phosphorus in the shell of T. retusa correlates well with that of protein indicating the presence of phosphorylated proteins in the periostracum, the sheaths surrounding the calcite fibres and the interface between the primary and secondary layer.     

Flexural isostatic response of the Alps to increased Quaternary erosion recorded by foreland basin remnants,SE France

We test the hypothesis that flexural isostatic compensation of the mass removed by enhanced Quaternary erosion is responsible for uplift of the Western European Alps and their forelands. We use two well‐preserved and well‐dated (1.8 Ma) abandonment surfaces of foreland basin remnants in SE France (the Chambaran and Valensole plateaux) as passive benchmarks for tilting of the foreland. Estimating their initial slope from morphometric scaling relationships, we determine bulk post‐depositional tilting of 0.5–0.8% for these surfaces. The calculated isostatic response of the Alpine lithosphere to erosional unloading, using the method recently proposed by Champagnac et al. [Geology 35 (2007) 195–198] , yields a predicted tilting of 0.3–0.4% in the considered areas, explaining approximately half of the determined post‐depositional tilting. Such long‐term deformation being insensitive to cyclic loading/unloading because of glaciations, we suspect the other half to be related to as yet undetermined long‐wavelength and long‐lived tectonic process(es).     

Fossil organic matrices of the Callovian aragonitic ammonites from Lukow (Poland): location and composition

The micro- and nanostructures of modern and fossil aragonitic nacreous layers of cephalopod shells were studied with scanning electron microscope (SEM) and atomic force microscope (AFM). The nacreous tablets are organized in sectors, composed of acicular units. The acicular units are composed of small granules. The fossil and modern shells show some differences in granule size, but the granules are surrounded by a thin envelope in both samples. Electrophoretic and amino-acid compositions show that organic matrices are present in the fossil shells. Thus, the organic nature of the granule envelopes can be inferred from the two analytical approaches. The AFM microscopy allows us to study the nanostructures of the recent and fossil hard tissues and to observe the diagenetic changes of both the mineral and organic components.     

XANES mapping of organic sulfate in three scleractinian coral skeletons

The presence and localization of organic sulfate within coral skeletons are studied by using X-ray absorption near edge structure spectroscopy (XANES) fluorescence. XANES spectra are recorded from four reference sulfur-bearing organic molecules: three amino acids (H-S-C bonds in cysteine; C-S-C bonds in methionine; one disulfide bond C-S-S-C bonds in cystine) and a sulfated sugar (C-SO₄ bonds in chondroitin sulfate). Spectral responses of three coral skeletons show that the sulfated form is extremely dominant in coral aragonite, and practically exclusive within both centres of calcification and the surrounding fibrous tissues of coral septa. Mapping of S-sulfate concentrations in centres and fibres gives us direct evidence of high concentration of organic sulfate in centres of calcification. Additionally, a banding pattern of S-sulfate is visible in fibrous part of the coral septa, evidencing a biochemical zonation that corresponds to the step-by-step growth of fibres.     

Oxygen isotopic signature of the skeletal microstructures in cultured corals: Identification of vital effects

In order to identify vital effect on oxygen isotopic ratio, we analyzed at micrometer size scale skeleton microstructures of a scleractinian coral Acropora, cultured under constant conditions. Measurements focused on the two crystalline units highlighted different isotopic signatures. Massive crystals (centers of calcification: COC) exhibit quasi-constant lowest values whereas fibers, the dominant units exhibit scattered distribution with amplitude of up to 5‰. Fiber oxygen isotopic ratios (δ¹⁸O) range from values similar to instantaneous deposition to equilibrium value. By comparing data obtained on the Acropora specimen and deep-sea corals grown under well constrained conditions, we infer that the scattered δ¹⁸O aragonite fibers indicate precipitation through kinetic precipitation. Thus, we argue for inherent biological feature typical to all coral genera. Modalities of COC formation remain ignored.The different isotopic signature of two mineral microstructures present in close proximity in coral skeleton can only be explained by compartment depositions related to different organic environments. Indeed, multiple secondary electron microscopy (SEM) observations favor interaction between mineral and organic matrix surface. Moreover, atomic forcing microscopy (AFM) investigations demonstrated thermodynamic changes induced by mineralization in presence of organic compounds. The combination of our results with previous published ones from biological studies, allows us proposing a consistent model of fiber skeleton formation. The prerequisite step of mineral growth unit precipitation would be initiated by organic matrix secretion, which defines spatial extension. Specific carriers supply ionic compounds of the crystals to ensure local supersaturation. However, possibly controlled by organic molecules, ionic amount would be limited, implying the supersaturation decline over the time. This could explain the progressive decrease of the coral growth rate. In this case, vital effect should not only bias isotopic fractionation through biological activity but the mechanism of skeleton deposition is imposed by specific chemical and/or physical conditions due to the presence of organic molecules. These conclusions derive from observations performed at high resolution.Therefore, isotopic ratio measured on millimeter scale for paleoclimatic purposes, result of the average of strongly heterogeneous values. It could explain vital effects shown by geochemical time series derived from tropical coral skeleton, including the high species and/or colony variability.     

In situ measurements of oxygen isotopic composition in deep-sea coral, Lophelia pertusa: Re-examination of the current geochemical models of biomineralization

We present ion microprobe measurements of oxygen isotopic compositions in the deep-sea coral Lophelia pertusa. Compared to bulk skeletal aragonite fibres, the EMZ (early mineralization zone), near the inside of the calyx, was systematically depleted in ¹⁸O. Rayleigh fractionation from a semi-closed fluid reservoir does not explain this and other geochemical differences. Furthermore, pH values estimated from skeletal δ¹¹B data are inconsistent with the idea that EMZ (or centres of calcification) ¹⁸O depletion reflects a more alkaline calcification environment. Our data, combined with microstructural and geochemical observations, indicate that the aragonitic fibres and EMZ are formed by a compartmentalized mineralization calicoblastic ectoderm, which exerts strong biological control on the composition of the skeleton. Hence, we propose a new model whereby amorphous calcium carbonates (ACC) are precursors to the EMZ, whereas the fibre precipitation is probably governed by kinetic processes.     

Early oxidation of organic matter in pelagic sediments of the eastern equatorial Atlantic: suboxic diagenesis

Pore water profiles of total-CO₂, pH, PO^3?₄, NO^?₃ plus NO^?₂, SO^2?₄, S^2?, Fe²⁺ and Mn²⁺ have been obtained in cores from pelagic sediments of the eastern equatorial Atlantic under waters of moderate to high productivity. These profiles reveal that oxidants are consumed in order of decreasing energy production per mole of organic carbon oxidized (O₂ > manganese oxides ~ nitrate > iron oxides > sulfate). Total CO₂ concentrations reflect organic regeneration and calcite dissolution. Phosphate profiles are consistent with organic regeneration and with the effects of release and uptake during inorganic reactions. Nitrate profiles reflect organic regeneration and nitrate reduction, while dissolved iron and manganese profiles suggest reduction of the solid oxide phases, upward fluxes of dissolved metals and subsequent entrapment in the sediment column. Sulfate values are constant and sulfide is absent, reflecting the absence of strongly anoxic conditions.     

Evolution: disjunct degeneration of immunological determinants

The dissolution of calcified invertebrate skeletons releases an elaborate mixture of proteins, glycoproteins and polysaccharides. These skeletal matrix macromolecules are thought to play a major role in calcification and were widely used for phylogenetical studies. We tested the reactivity of water-soluble macromolecules from a wide range of invertebrate skeletons with two antisera raised against the shell matrix of the bivalve, Pinna nobilis. Projections of our results on the phylogenetical tree of Starobogatov (1992) show for the first time that, during evolution, antigenic determinants may degenerate in some stocks while they remain intact in others. The phylogenetic implications of these patterns of disjunct degeneration are discussed.     

A deep-sea in-situ suspended sediment sampling system

A prototype deep pump filtration system, designed to sample suspended particulate matter in the deep sea, has been developed for use with an in-situ optical nephelometer used to locate zones of high particulate concentration. The filtration system, which has essentially an unlimited depth capability, can sample large volumes of water and is limited only by the concentration of the suspended load and the clogging characteristics of the filter, thereby being ideally suited for use in areas of extremely low particulate concentration. In its present configuration, the unit is capable of collecting as much as 200 mg of suspended sediment per lowering. The system is compact in design and may easily be integrated with any instrument platform, or used independently. In addition, the membrane filtration method utilized provides a convenient means of sample handling during analysis with a minimum of contamination.     

Spectral analysis of late Pleistocene-Holocene sediments

Spectral analysis of deep-sea sediments indicates that the fluctuations in compositional parameters are not random fluctuations with time. Spectra show significant peaks representing periodicities in the data of 380, 1300, and 2600 years. Two of these periods are similar to periods reported in ¹⁴C fluctuations. Analysis of a paleotemperature curve from the North Atlantic shows that the characteristics of the fluctuations within interglacial and glacial stages of the climate are similar, and that the spectrum has a significant peak at 2600 years.