The origin and significance of euhedral apatite crystals on conodonts

Crystal overgrowth on fossil remains is well-documented in the literature. Attention has specifically focused on bioapatite (i.e., an apatite of biochemical origin regardless of post-mortem changes) configurations, in order to decipher any possible relation to fossilization/diagenesis. This study investigates the Rare Earth Element (REE) and other High-Field-Strength Element (HFSE) composition of euhedral crystals formed on the surface of conodont elements compared with that of crystal-free surfaces. Euhedral crystals are by definition crystals characterized by sharp faces, developing solids that, for apatite, assume the form of hexagonal prisms, reflecting its crystal symmetry. Late Ordovician (Amorphognathus ordovicicus Zone) conodonts from two localities in Sardinia and the Carnic Alps (Italy) are herein investigated. Conodont elements reveal the occurrence of smooth surfaces and surfaces partially covered with euhedral crystals. Since euhedral crystals did not reasonably grow during the organism’s lifetime, the REE and HFSE analysis can provide important insights into the crystal growth process. The experimental results indicated a substantial contribution of diagenetic imprinting for all the analyzed material, although more evident on euhedral crystals that are significantly enriched in middle and, subordinately, in heavy REE with respect to smooth surfaces. The positive correlations between La + Th vs log[ΣREE] and Ce + Th vs log[ΣREE] could support the hypothesis that the neoformed euhedral crystals grew also by depleting the pristine bioapatite of the conodont elements. Nevertheless, the occurrence of two types of apatite cannot be ruled out: euhedral crystals as neoformed products of diagenetic processes and smooth surfaces as remains of the pristine conodont bioapatite after diagenesis

Diagenesis does not invent anything new: Precise replication of conodont structures by secondary apatite

Conodont elements are important archives of sea/pore water chemistry yet they often exhibit evidence of diagenetic mineral overgrowth which may be biasing measurents. We decided to investigate this phenomenon by characterising chemically and crystallographically, the original biomineral tissue and the diagenetic mineral nature of conodont elements from the Ordovician of Normandy. Diagenetic apatite crystals observed on the surface of conodont elements show distinctive large columnar, blocky or web-like microtextures. We demonstrate that these apatite neo-crystals exhibit the same chemical composition as the original fossil structure. X-ray microdiffraction has been applied herein for the first time to conodont structural investigation. Analyses of the entire conodont element surface of a variety of species have revealed the existence of a clear pattern of crystal preferred orientation. No significant difference in unit cell parameters was documented between the newly formed apatite crystals and those of the smooth conodont surfaces, thus it emerges from our research that diagenesis has strictly replicated the unit cell signature of the older crystals

Crystal structure and crystal chemistry of fluorannite and its relationships to annite

This contribution deals about the crystal chemical characterization of fluorannite from Katugin Ta-Nb deposit, Chitinskaya Oblast’, Kalar Range, Transbaikalia, Eastern-Siberian Region, Russia. The mineral chemical formula is (K0.960Na0.020Ba0.001) (Fe2+2.102Fe3+0.425Cr3+0.002Mg0.039Li0.085Ti0.210Mn0.057) (Al0.674 Si3.326) O10 (F1.060OH0.028O0.912). This mica belongs to 1M polytype (space group C2/m) with layer parameters a = 5.3454(2) Å, b = 9.2607(4) Å, c = 10.2040(5) Å, beta = 100.169(3)°. Structure refinement, using anisotropic displacement parameters, converged at R = 0.0384. When compared to annite, fluorannite shows a smaller cell volume (Vfluorannite = 497.19 Å3; Vannite = 505.71 Å3), because of its smaller lateral dimensions and its reduced c parameter. The flattening of the tetrahedral basal oxygen atoms plane decreases with F content, together with the A-O4 distance (i.e., the distance between interlayer A cation and the octahedral anionic position) because of the reduced repulsion between the interlayer cation and the anion sited in O4

Mineralogy and crystallization patterns in conodont bioapatite from first occurrence (Cambrian) to extinction (end-Triassic)

Bioapatite represents an important acquisition in the evolution of life, both in the seas and on land. Vertebrates applied calcium-phosphate biominerals to grow their skeletal support and to shape their teeth, while some invertebrates sheltered their soft parts within apatite shells. Conodonts were the first among vertebrates to experiment with skeletal biomineralization of tooth-like elements in their feeding apparatus. Spanning a time record of over 300 million years, they offer a unique tool to test possible variation in bioapatite structure from the experimentation of a very primitive biomineralization type to a more evolute pattern just before going extinct. X-ray microdiffraction carried out through an X-ray micro-diffractometer, integrated with environmental scanning electron microscopy coupled with chemical microanalyses (ESEM-EDX), has been applied in this study to investigate conodont element crystal structure throughout the entire stratigraphic range of these organisms. In particular, bioapatite crystallographic cell parameters have been calculated for about one hundred conodont elements ranging from the late Cambrian to the Late Triassic. Resulting data clearly indicate two distinct distribution plots of cell parameters for paraconodonts and euconodonts. In contrast, age, taxonomy, geographic provenance and CAI do not affect the dimension of the bioapatite crystal cells. Conodont bioapatite crystallographic cell parameters have been compared with cell parameters resulting from phosphatic/phosphatized material (ostracodes, brachiopods, bryozoans, and fish teeth) present in the same residues producing conodonts. Resulting values of the cell parameters are, in general, mainly correlated with the type of organisms even if, for some of them, a correlation also with age cannot be completely ruled out. According to our data, primary bioapatite appears to imprint a key signature on fossil crystal-chemistry (crystal structure and major chemical element contents), while the contribution of fossilization and diagenetic processes seems less relevant

HOW DID VERTEBRATES SHARPEN THEIR TEETH? A NEW PERSPECTIVE IN BIOAPATITE ANALYSIS

HOW DID VERTEBRATES SHARPEN THEIR TEETH? A NEW PERSPECTIVE IN BIOAPATITE ANALYSI

Zooming in REE and Other Trace Elements on Conodonts: Does Taxonomy Guide Diagenesis?

Conodont elements are calcium phosphate (apatite structure) mineralized remains of the cephalic feeding apparatus of an extinct marine organism. Due to the high affinity of apatite for rare earth elements (REE) and other high field strength elements (HFSE), conodont elements were frequently assumed to be a reliable archive of sea-water composition and changes that had occurred during diagenesis. Likewise, the crystallinity index of bioapatite, i.e., the rate of crystallinity of biologically mediated apatite, should be generally linearly dependent on diagenetic alteration as the greater (and longer) the pressure and temperature to which a crystal is exposed, the greater the resulting crystallinity. In this study, we detected the uptake of HFSE in conodont elements recovered from a single stratigraphic horizon in the Upper Ordovician of Normandy (France). Assuming therefore that all the specimens have undergone an identical diagenetic history, we have assessed whether conodont taxonomy (and morphology) impacts HFSE uptake and crystallinity index. We found that all conodont elements are characterized by a clear diagenetic signature, with minor but significant differences among taxa. These distinctions are evidenced also by the crystallinity index values which show positive correlations with some elements and, accordingly, with diagenesis; however, correlations with the crystallinity index strongly depend on the method adopted for its calculation

Ipsilateral evaluation of the transverse sinus: Transcranial color-coded sonography approach in comparison with magnetic resonance venography

SummaryIntroductionThe ultrasound examination of intracranial venous structures by transcranial color-coded sonography (TCCS) is a validated and standardized application. Similarly some intracranial venous sinuses are known for their relatively low insonation rate, as straight sinus (SRS) and transverse sinus (TS), ranging from 35% to 73%. The relatively high frequency of hypoplasia of TS can partially take account for these data. The aim of this study is to evaluate the feasibility of this approach in a standard TCCS examination, in comparison with magnetic resonance (MR) findings by using the Virtual Navigator system.Patients and methodsThe standardized approach to the TS was a contralateral insonation, starting to the SRS plane and angulating downwards the probe. In this way it is possible to insonate the proximal segment of the contralateral TS. We proposed a new approach with an extreme downwards tilting and a slow opposite angulation of the probe for examining the ispilateral TS. Forty consecutive subjects were chosen among patients who underwent standard TCCS examinations at our lab and had a suitable temporal acoustic window, and a recently performed MR venography. The contralateral TS insonation rate was compared with the ipsilateral one.Results and discussionThe insonation rate was 61/80 (76.25%) for the contralateral TS and 75/80 (93.75%) for the ipsilateral approach. Two of 5 not detectable TS were aplasic in MR venography and the others were not identified by a poor acoustic window.ConclusionsThe ipsilateral approach could be associated to the contralateral standard study for insonating the TS