Magnesium and sulphur in the calcite shells of two brachiopods, Terebratulina retusa and Novocrania anomala

This study determines the distribution of magnesium and sulphur in the shells of two species of brachiopod from the same environment to highlight environmental and biological influences on shell composition. In Terebratulina retusa there are differences in magnesium concentration between the primary layer and the outer and inner regions of the secondary layer. In contrast, Novocrania anomala has a shell composed of high magnesium calcite and there is no significant difference in magnesium concentration between the primary and the secondary shell layers. Sulphur provides an indication of the distribution of sulphated organic matrix within the shells of T. retusa and N. anomala . In T. retusa the distribution of magnesium and sulphur correlates across the shell; however, there is no evidence for a relationship between magnesium and sulphur distribution in N. anomala . The relationship between magnesium and sulphur in T. retusa indicates that a proportion of the magnesium content of the shell is associated with the sulphated fraction of the organic matrix. In these two species of brachiopod, from the same environment, magnesium and organic concentration and distribution are very different, emphasizing the importance of fully understanding the factors that control biomineral composition before the application of these biominerals to environmental studies.     

Mineral phase in linguloid brachiopod shell: Lingula adamsi

The linguloid brachiopod shell family has been the focus of several studies because of the similarity in the composition of the mineral phase of these shells to that of human bone. However, ultrastructural features of Lingula shells have not yet been fully demonstrated at high magnification using Transmission Electron Microscopy (TEM) and Electron Diffraction. Ultrastructural characterization of the mineral phase in Lingula shells will improve our understanding of the biomineralization processes and mineral/organic interaction in more complex systems such as in bone or in other human mineralized tissues. In this study, the mineral phase of Lingula adamsi was characterized using a combination of ultrastructural and crystallographic techniques. The results showed that L. adamsi shells consist of apatite crystals of varying size, shape, and orientation in different areas of the shell. The c-axis of apatite was parallel to the shell surface and crystals were organized in different laminae. Compared to trabecular bovine bone, L. adamsi shells demonstrated a higher crystallinity and a lower amount of carbonate and organic compounds. This study therefore demonstrated how dissimilar organic matrix between L. adamsi shell and trabecular bone can modify the ultrastructural characteristics of apatite crystals in these two biomineralized tissues.     

Shell microstructure and mineralogy of the Littorinidae: ecological and evolutionary significance

An examination of the shell microstructure and mineralogy of species from 30 of the 32 genera and subgenera of the gastropod family Littorinidae shows that most species have a shell consisting of layers of aragonitic crossed-lamellar structure, with minor variations in some taxa. However, Pellilitorina, Risellopsis and most species of Littorina have partly or entirely calcitic shells. In Pellilitorina the shell is made entirely of calcitic crossed-foliated structure, while in the other two genera there is only an outer calcitic layer of irregular-prismatic structure. A cladistic analysis shows that the calcitic layers have been independently evolved in at least three clades. The calcite is found only in the outermost layers of the shell and in species inhabiting cooler waters of both northern and southern hemispheres. Calcium carbonate is more soluble in cold than warm water and, of the two polymorphs, calcite is about 35% less soluble than aragonite. We suggest that calcitic shell layers are an adaptation of high latitude littorinids to resist shell dissolution.     

Mechanical properties of modern calcite- (Mergerlia truncata) and phosphate-shelled brachiopods (Discradisca stella and Lingula anatina) determined by nanoindentation

We measured distribution patterns of hardness and elastic modulus by nanoindentation on shells of the rhynchonelliform brachiopod Mergerlia truncata and the linguliform brachiopods Discradisca stella and Lingula anatina. The rhynchonelliformea produce calcitic shells while the linguliformea produce chitinophosphatic shells. Dorsal and ventral valves, commissure and hinge of the calcitic shell of M. truncata show different nanohardness values (from 2.3 to 4.6 GPa) and E-modulus (from 52 to 76 GPa). The hardness of the biocalcite is always increased compared to inorganic calcite. We attribute the effects to different amounts of inter- and intracrystalline organic matrix. Profiles parallel to the radius of curvature of the valves cutting through the different layers of shell material surprisingly show quite uniform values of nanohardness and modulus of elasticity. Nanoindentation tests on the chitinophosphatic brachiopods D. stella and L. anatina reflect the hierarchical structure composed of laminae with varying degree of mineralization. As a result of the two-phase composite of biopolymer nanofibrils reinforced with Ca-phosphate nanoparticles, nanohardness, and E-modulus correlate almost linearly from (H = 0.25 GPa, E = 2.5 GPa) to (H = 2.5 GPa, E = 50 GPa). The mineral provides stiffness and hardness, the biopolymer provides flexibility; and the composite provides fracture toughness. Gradients in the degree of mineralization reduce potential stress concentrations at the interface between stiff mineralized and soft non-mineralized laminae. For the epibenthic chitinophosphatic D. stella the lamination is also present but less pronounced than for the infaunal L. anatina, and the overall distribution of material strength in the cross-sectional profile shows a maximum in the center and a decrease towards the inner and outer shell margins (modulus of elasticity from 30 to 12 GPa, hardness from 1.7 to 0.5 GPa). Accordingly, the two epibenthic forms, calcitic M. truncata and chitinophosphatic D. stella display fairly bulky (homogeneous) nanomechanical properties of their shell materials, while the burrowing infaunal L. anatina is distinctively laminated. The strongly mineralized laminae, which provide the strength to the shell, are also brittle, but keeping them as thin as possible, allows some bending flexibility. This flexibility is not required for the epibenthic life style.     

Shell mineralogical trends in epifaunal Mesozoic bivalves and their relationship to seawater chemistry and atmospheric carbon dioxide concentration

The Late Triassic-Early Jurassic change from aragonite- to calcite-facilitating conditions in the oceans, which was caused by a decrease of the Mg²⁺/Ca²⁺ ratio of seawater in combination with an increase of the partial pressure of carbon dioxide, also affected the shell mineralogy of epifaunal bivalves. In the “calcite sea” of the Jurassic and Cretaceous, the most diverse and abundant families of epifaunal bivalves had largely calcitic shells. Some of them, such as the Inoceramidae, acquired this shell mineralogy earlier in Earth's history but did not significantly diversify until the onset of “calcite sea” conditions. Others, however, replaced aragonite by calcite in their shell at the beginning of the Jurassic, as shown for the Ostreidae, Gryphaeidae, Pectinidae, Plicatulidae, and Buchiidae. In these families, replacement of aragonite by calcite took place in the middle and inner layer of the shell and was not associated with changes in morphology and life habit. It is therefore proposed that lower metabolic costs rather than higher resistance against dissolution or advantageous physical properties triggered the calcite expansion in their shells. This explanation fits well the observation that clades of thin-shelled bivalves were less affected by the change of seawater chemistry. Thick-shelled clades, by contrast, may suffer a severe decline in diversity until they adapt their shell mineralogy, as demonstrated by the Hippuritoida: The diversity of the Megalodontoidea, which failed to adapt their shell mineralogy to “calcite sea” conditions, dramatically decreased at the end of the Triassic, whereas their descendents became dominant carbonate producers during the Late Mesozoic after they acquired a calcitic outer shell layer in the Late Jurassic. These examples indicate that changes in the seawater chemistry and in the partial pressure of carbon dioxide are factors that influence the diversity of carbonate-secreting animals, and, as in the case of the decline of the Megalodontoidea, may contribute to mass extinctions.     

Lingulid shell mediation in clay formation

Organophosphatic shells of the brachiopod Lingula squarniformis , collected from Scottish Lower Carboniferous shales and mudstones of intertidal to sublittoral provenance, have been studied to ascertain chemico-structural changes resulting from fossilization. Enough original shell has been preserved at ultrastructural and molecular levels to confirm that Carboniferous and Recent integuments are homologous with stratiform successions of apatitic to organic laminae forming rhythmic sets. One of the main organic constituents, the acidic, hydrophilic gel glycosaminoglycans (GAGs), is the dominant component towards the tops of rhythms. During fossilization of the Carboniferous shells, GAGs degraded incrementally without disturbing apatitic ultrastructures, and the spaces so created became partly filled with sheets of recrystal-lized apatite with some kaolinite or with books and plates of kaolinite. The kaolinite in the shells contrasts with the illite of the entombing sediments and suggests that degrading acidic GAGs mediated in clay formation in situ . The sediments also contain framboidal pyrite, which is virtually absent from the shells themselves but is usually even more abundant, with a greater range of trace metals, in the sedimentary fills of complete shells. This imbalance suggests mediation by another gel, the glycocalyx, secreted by the inner epithelium of the brachiopod mantle. The glycocalyx would have lined the shell interior and could have served as a sorption film for dissolved metals precipitated as compounds on decomposition of body tissue.     

The brachiopod <Emphasis Type="Italic">Eoobolus</Emphasis> from the Early Cambrian Mural Formation (Canadian Rocky Mountains)

The Early Cambrian brachiopod, Eoobolus, is one of the first representatives of the superfamily, Linguloidea, the defining characteristics of which include the classical morphology of oval shells and a pedicle that emerges from between the two valves. The material described here from the Mural Formation (Jasper National Park, Canadian Rocky Mountains) provides well-preserved muscle scars and larval shells that allow a discussion of the muscle system and the larval morphology of Eoobolus. The dorsal larval shell exhibits a morphology similar to other Cambrian linguloids, but also to paterinids, Mickwitzia muralensis, and some rhynchonelliforms. This suggests that there was a lesser degree of disparity among brachiopod larvae in the Cambrian than there is today. The muscle system of Eoobolus is similar to other linguloids, but differs from that of Recent lingulids and discinids by having one or two more pairs of oblique muscles. New data on the distribution of features characteristic of the family Eoobolidae question the validity of this family.     

THE ENIGMATIC EARLY CAMBRIAN SALANYGOLINA– A STEM GROUP OF RHYNCHONELLIFORM CHILEATE BRACHIOPODS?

Abstract:  New material of the enigmatic brachiopod Salanygolina obliqua Ushatinskaya from the Early Cambrian of Mongolia shows that it has a colleplax – a triangular plate – in the umbonal perforation, which is enlarged by resorption. This structure is otherwise only known from the equally enigmatic Palaeozoic orders Chileida and Dictyonellida (Rhynchonelliformea, Chileata). The colleplax in Salanygolina is here considered to be homologous with that of the chileates. Salanygolina is also provided with a ridge-like pseudodeltidium, which is another chileate feature. Other characters of Salanygolina , like the radial arrangement of adductor muscle scars and postero-medially placed internal oblique muscles are characteristic of chileates, but also found in the paterinates. In contrast, mixoperipheral dorsal valves with low rudimentary interareas are well known in paterinates, but not yet recorded from chileates. Thus, Salanygolina shows a mosaic combination of morphologic characters, known both from the paterinates and chileates, indicating that it may represent a stem group of the rhynchonelliform chileate brachiopods. The laminar phosphatic secondary shell of Salanygolina is composed of closely packed and nearly identical hexagonal prisms, oriented with their long axis normal to the laminae in a honeycomb pattern. The prism walls appear to have originally been composed of organic membranes and might represent precursors of the organic sheaths of calcite fibers that are typical of calcitic shells with a fibrous microstructure.     

A Stem Group Brachiopod From The Lower Cambrian: Support For A Micrina (Halkieriid) Ancestry

The shell structure of the Lower Cambrian Mickwitzia , a bilaterally symmetrical bivalve hitherto doubtfully assigned to the Brachiopoda, confirms that the genus shares characters with linguliform brachiopods. The columnar lamination of its organophosphatic shell is homologous with that characterizing acrotretides. The shell, however, is also pervaded by striated apatitic tubes indistinguishable from those permeating the sclerites of the problematic organophosphatic, laminar–shelled Micrina which is close to Halkieria . No crown group brachiopods have such tubes that are presumed to have contained setae. The presence of both these features in the Mickwitzia shell suggests that the stock is a stem group brachiopod with a halkieriid ancestry.     

An intracrystalline chromoprotein from red brachiopod shells: implications for the process of biomineralization.

1. The red colour of some terebratulid brachiopod shells is caused by a small chromoprotein that occurs within the calcium carbonate matrix of the shell. 2. This carotenoid-protein complex was isolated from within the calcite shell of three different brachiopod genera and may therefore be involved in the process of biomineralization. 3. The apparent molecular weight of this protein, as judged by SDS-PAGE, is 6.5 kDa. 4. The partial N-terminal amino acid sequence of the protein is virtually identical in three different brachiopod genera, indicating homology. 5. Two carotenoids are present in Terebratella sanguinea: canthaxanthin and the tentatively identified monoacetylinic analogue of astaxanthin.     

Endolithic micro-organisms silicification of a bivalve fauna from the Silurian of Gotland

The silicified Wenlockian bivalve shells at Möllbos have been fragmented to a considerable extent. Shells which were broken prior to silicification exhibit possible original shell layers while those which were fragmented during laboratory treatment show no primary structures. The fauna at Möllbos was attacked by endolithic micro-organisms. The borings of these were then coated with a carbonate envelope. After burial the unattacked original shell material was dissolved the envelope silicified. Later, empty moulds were subsequently filled with drusy calcite occasionally with quartz crystals. A third silicification went occurred at a later diagenetic stage when matrix had become lithified.     

Breaking the long-standing morphological paradigm: Individual prisms in the pearl oyster shell grow perpendicular to the c-axis of calcite

Cross-sections of calcitic prismatic layers in mollusk shells, cut perpendicular to growth direction, reveal well-defined polygonal shapes of individual “grains” clearly visible by light and electron microscopy. For several kinds of shells, it was shown that the average number of edges in an individual prism approaches six during the growth process. Taking into account the rhombohedral symmetry of calcite, often presented in hexagonal axes, all this led to the long-standing opinion that calcitic prisms grow along the c-axis of calcite. In this paper, using X-ray diffraction and electron backscatter diffraction (EBSD), we unambiguously show that calcitic prisms in pearl oyster Pinctada margaritifera predominantly grow perpendicular to the c-axis. The obtained results imply that the hexagon-like habitus of growing crystallites may be not necessarily connected to calcite crystallography and, therefore, other factors should be taken into consideration. We analyze this phenomenon by comparing the organic contents in Pinctada margaritifera and Pinna nobilis shells, the later revealing regular growth of calcitic prisms along the c-axis.     

Diagenetic fate of bioapatite in linguliform brachiopods: multiple apatite phases in shells of Cambrian lingulate brachiopod Ungula ingrica (Eichwald)

Fossil skeletal apatites vary in their composition and can yield mixed biochemical, environmental and diagenetic information. Thus, it is important to evaluate the diagenesis spatially inside the skeleton. We study the cross sections of shells of the Furongian lingulate brachiopod Ungula ingrica from Estonia using the Attenuated Total Reflectance – Fourier Transform Infrared (ATR‐FTIR) microspectroscopic and energy dispersive spectroscopic (EDS) mapping and show for the first time that different structural laminae of the shell have different chemical compositions. Compact laminae are rich in PO₄^3?, Na, Mg and poor in F and Ca. Porous (baculate) laminae are rich in carbonate anions, Ca and F, but contain less Na and Mg. The ATR‐FTIR spectra show further differences in the ν₂ carbonate region, where the IR band at 872 cm^?1 in compact laminae is replaced by a strong band at 864 cm^?1 in baculate laminae. The changes in shell apatite suggest different origins of the apatite phases. Compact laminae are likely chemically less altered and could potentially carry more reliable palaeoenvironmental or geochemical information than the apatite in baculate laminae, which is mostly authigenic in its origin.     

A New Approach for the Determination of Ammonite and Nautilid Habitats

Externally shelled cephalopods were important elements in open marine habitats throughout Earth history. Paleotemperatures calculated on the basis of the oxygen isotope composition of their shells can provide insights into ancient marine systems as well as the ecology of this important group of organisms. In some sedimentary deposits, however, the aragonitic shell of the ammonite or nautilid is poorly or not preserved at all, while the calcitic structures belonging to the jaws are present. This study tests for the first time if the calcitic jaw structures in fossil cephalopods can be used as a proxy for paleotemperature. We first analyzed the calcitic structures on the jaws of Recent Nautilus and compared the calculated temperatures of precipitation with those from the aragonitic shell in the same individuals. Our results indicate that the jaws of Recent Nautilus are secreted in isotopic equilibrium, and the calculated temperatures approximately match those of the shell. We then extended our study to ammonites from the Upper Cretaceous (Campanian) Pierre Shale of the U.S. Western Interior and the age-equivalent Mooreville Chalk of the Gulf Coastal Plain. In the Pierre Shale, jaws occur in situ inside the body chambers of well-preserved Baculites while in the Mooreville Chalk, the jaw elements appear as isolated occurrences in the sediment and the aragonitic shell material is not preserved. For the Pierre Shale specimens, the calculated temperatures of well-preserved jaw material match those of well-preserved shell material in the same individual. Analyses of the jaw elements in the Mooreville Chalk permit a comparison of the paleotemperatures between the two sites, and show that the Western Interior is warmer than the Gulf Coast at that time. In summary, our data indicate that the calcitic jaw elements of cephalopods can provide a reliable geochemical archive of the habitat of fossil forms.     

Microscopic imprints on the juvenile shells of Palaeozoic linguliform brachiopods

The juvenile shell of living discinid brachiopods is composed of valvular mosaics of rhombic, micrometric–sized siliceous tablets. The tablets are shed in adult growth stages leaving shallow imprints on the primary layer of the organophosphatic mature shell, which occur on an upper Silurian discinoid. Imprints also indent the first–formed shells of over 100 lingulate genera, including all acrotretides and Paterula . No micrometric bodies that could have made these imprints are known, but their structure and composition can be inferred from imprint morphology. Diagnostic features of imprints as casts include constancy of shape and size, and rigidity of the indenting bodies relative to the rheology of the polymerizing primary layer of chitin, glycosaminoglycans (GAGs) and apatite, in which they were embedded. Three kinds of discrete structures are distinguishable. Nanometric–sized, basinal pits that may be compound or deformed, are assumed to be casts of mucinous vesicles. Larger, flat–based and hemispherical imprints were almost certainly made by biomineralized discoids and spheroids. Additional evidence that discoids and spheroids were more soluble than apatite suggests that they were calcitic. Mineralized mosaics could have protected pelagic juveniles from solar radiation in the early Palaeozoic when the ozone layer was more rarified than today.     

Shell microstructure in the Permian nonmarine bivalve Palaeomutela Amalitzky: Revision of the generic diagnosis

The microstructure of aragonitic and calcitic shells of the genus Palaeomutela Amalitzky, 1891 is examined. The aragonitic shell consists of three main layers, each is distinguished by certain crossed lamellar microstructure: comarginal, radial, and complex. As aragonite is recrystallized into pelitic calcite, microstructural shell features are preserved. Many species of Palaeomutela from localities of different age display the same microstructural pattern, which is possible to regard as a character of generic rank.     

Study of fossil and recent brachiopods,using a skyscan 1172 X-ray microtomograph

Fossil and recent brachiopods were studied with the aid of a Skyscan 1172 microtomograph. The capabilities of this method at different stages of studying, X-ray scanning and producing slices and 3D models are described. The method enables the study of punctuation, microornamentation, and inner structures of the brachiopod shells and soft tissues. The contrast of shell structures of fossil brachiopods is discussed; it depends on differences in the mineral composition of the shell and surrounding matter. This method allows studying the inner structure of the holotypes of brachiopod species without damaging their shells. The data on the efficiency of the method are provided.     

The development of growth lines on articulate brachiopods

Three types of growth lines are recognised on articulate brachiopod shells: (1) very fine diurnal growth lines formed by calcite increments at the shell margin, (2) seasonal growth lines, formed by inward reflection (doubling back) of the mantle edge, seen as concentric steps on the shell surface and marked by re-orientation of growth vectors evidenced by secondary shell fibres, (3) disturbance lines, formed by abrupt regression of the mantle edge, also seen as concentric steps on the shell surface, but indicated by a dislocation in the shell fabric. Lamellose and spinose ornaments of the sort seen in Tegulorhynchia are essentially genetically controlled. Periodic outgrowths from the outer mantle lobe secrete frills of primary shell that project from the shell surface and form short hollow spines where they cross the radial ornament. In longitudinal section spine formation is seen to involve gradual increase in the rate of secretion of primary shell followed by retraction, and often collapse, of the mantle outgrowth, accompanied by regression. Reflection of the mantle edge usually follows spine formation.     

EARLY CAMBRIAN BRACHIOPODS FROM NORTH-EAST GREENLAND

Abstract:  A diverse assemblage of late Early Cambrian brachiopods is described from the Bastion and Ella Island formations of North-East Greenland. The fauna includes nine species, representing all three extant brachiopod subphyla in addition to the stem group brachiopod Mickwitzia cf. occidens . Four linguliforms: Eoobolus priscus , Botsfordia caelata , Micromitra bella , Vandalotreta sp., three rynchonelliforms: Obolella crassa , Kutorgina reticulata , and an unidentified chileid plus a possible craniiform species occur. The fauna shows similarities to late Early Cambrian (Dyeran Stage) brachiopod faunas of eastern Canada and the United States, but also to faunas from the late Early Cambrian (Botomian–Toyonian equivalent) of Australia, Antarctica and Siberia.