Marine bivalve geochemistry and shell ultrastructure from modern low pH environments

Abstract. Bivalve shells can provide excellent archives of past environmental change but have not been used to interpret ocean acidification events. We investigated carbon, oxygen and trace element records from different shell layers in the mussels Mytilus galloprovincialis (from the Mediterranean) and M. edulis (from the Wadden Sea) combined with detailed investigations of the shell ultrastructure. Mussels from the harbour of Ischia (Mediterranean, Italy) were transplanted and grown in water with mean pHT 7.3 and mean pHT 8.1 near CO2 vents on the east coast of the island of Ischia. The shells of transplanted mussels were compared with M. edulis collected at pH ~8.2 from Sylt (German Wadden Sea). Most prominently, the shells recorded the shock of transplantation, both in their shell ultrastructure, textural and geochemical record. Shell calcite, precipitated subsequently under acidified seawater responded to the pH gradient by an in part disturbed ultrastructure. Geochemical data from all test sites show a strong metabolic effect that exceeds the influence of the low-pH environment. These field experiments showed that care is needed when interpreting potential ocean acidification signals because various parameters affect shell chemistry and ultrastructure. Besides metabolic processes, seawater pH, factors such as salinity, water temperature, food availability and population density all affect the biogenic carbonate shell archive.</jats:p

Microstructural data of six recent brachiopod species: SEM, EBSD, morphometric and statistical analyses

Here, we provide the dataset associated with the research article \ue2\u80\u9cMapping of recent brachiopod microstructure: A tool for environmental studies\ue2\u80\u9d [1]. We present original data relative to morphometric and statistical analyses performed on the basic shell structural units (the secondary layer fibres) of brachiopod shells belonging to six extant species adapted to different environmental conditions. Based on SEM micrographs of the secondary layer, fibres from ventral and dorsal valves, and from different shell positions, showing regular and symmetrical cross sectional outlines, were chosen for morphometric measurements using Adobe Photoshop CS6, Image-Pro Plus 6.0 and ImageJ. To work out the reliability of the measurements, the most significant parameters were tested for their probability density by distribution plots; for data visualization and dimension reduction, principal component analysis (PCA) was performed using R 3.3.0 [2] and independent-samples t-tests were performed using SPSS Statistics (IBM Version 22.0. Armonk, NY). Besides a quantitative analysis, a qualitative description of the shell microstructure is provided by detailed SEM imaging and EBSD measurements

Magnetic Field-Induced Superconductor-Insulator-Metal Transition in an Organic Conductor: An Infrared Magneto-Optical Imaging Spectroscopy

The magnetic field-induced superconductor-insulator-metal transition (SIMT) in partially deuterated $\kappa$-(BEDT-TTF)$_2$Cu[N(CN)$_2$]Br, which is just on the Mott boundary, has been observed using the infrared magneto-optical imaging spectroscopy. The infrared reflectivity image on the sample surface revealed that the metallic (or superconducting) and insulating phases coexist and they have different magnetic field dependences. One of the magnetic field dependence is SIMT that appeared on part of the sample surface. The SIMT was concluded to originate from the balance of the inhomogenity in the sample itself and the disorder of the ethylene end groups resulting from fast cooling.Comment: 5 pages, 5 figures, to appear in Phys. Rev.

Brachiopod-based oxygen-isotope thermometer: Update and review

In the early 1950\u2019s, McCrea and Epstein and co-workers laid the foundation for the oxygen isotope-based thermometers. Many variations of the thermometer have been since formulated based on synthetic and biogenic carbonates. Overall, the use and application of oxygen isotope thermometers must consider and be specific as to the mineralogy, and whether it is synthetic, abiogenic or biogenic carbonate. Here, we propose an updated and refined oxygen-isotope thermometer based on a large database of articulated brachiopods from high to low latitudes, cold to warm and shallow to deep-water regimes. In general, brachiopod-based oxygen isotopes are offset from abiogenic calcite precipitated in thermodynamic equilibrium by about -1 . They maintain this offset and that allows for the determination of robust ambient water temperatures over the full marine spectrum. Thus, the specific brachiopod-based oxygen-isotope thermometer applies, with few exceptions, to most modern articulated brachiopods, and potentially their ancient counterparts, and it is as follows: T\ub0C =17.3750 \u2013 4.2535 (\u3b4c-\u3b4w) + 0.1473 (\u3b4c-\u3b4w)2 (N=578, r2 = 0.980) Furthermore, it is imperative that mineralogy and taxa be considered for their appropriateness in the application of oxygen isotope thermometers on synthetic, abiogenic and biogenic marine carbonates. Articulated brachiopods are ideal recorders of oceanographic parameters due to their sessile nature, widespread distribution, high abundance in the Paleozoic and Mesozoic, high resilience to most environmental stresses (e.g., climate change - global warming, ocean acidification), and the resistance of the calcite shell \u2013 the archive \u2013 to post-depositional diagenetic alteration

Calcite distribution and orientation in the tergite exocuticle of the isopods porcellio scaber and armadillidium vulgare (Oniscidea, Crustacea) - A combined FE-SEM, polarized SCm-RSI and EBSD study

The crustacean cuticle is a bio-composite consisting of hierarchically organized chitin-protein fibres, reinforced with calcite, amorphous calcium carbonate and phosphates. Comparative studies revealed that the structure and composition of tergite cuticle of terrestrial isopods is adapted to the habitat of the animals, and to their behavioural patterns to avoid predation. In this contribution we use FE-SEM, polarized SCm-RSI and EBSD to investigate micro- and nano-patterns of mineral phase distribution and crystal orientation within the tergite cuticle of the two terrestrial isopod species Armadillidium vulgare and Porcellio scaber. The results show that the proximal regions of the exocuticle contain both calcite and ACC, with ACC located within the pore canals. Calcite forms hierarchically organised mesocrystalline aggregates of similar crystallographic orientation. Surprisingly, c-axis orientation preference is horizontal in regard to the local cuticle surface for both species, in contrast to mollusc and brachiopod shell structures in which the c-axis is always perpendicular to the shell surface. The overall sharpness of calcite crystal orientation is weak compared to that of mollusc shells. However, there are considerable differences in texture sharpness between the two isopod species. In the thick cuticle of the slow-walking A. vulgare calcite is more randomly oriented resulting in more isotropic mechanical properties of the cuticle. In contrast, the rather thin and more flexible cuticle of the fast- running P. scaber texture sharpness is stronger with a preference of c-axis orientation being parallel to the bilateral symmetry-plane of the animal, leading to more anisotropic mechanical properties of the cuticle. These differences may represent adaptations to different external and/or internal mechanical loads the cuticle has to resist during predatory attempts

Experimental diagenesis: insights into aragonite to calcite transformation of Arctica islandica shells by hydrothermal treatment

Abstract. Biomineralised hard parts form the most important physical fossil record of past environmental conditions. However, living organisms are not in thermodynamic equilibrium with their environment and create local chemical compartments within their bodies where physiologic processes such as biomineralisation take place. In generating their mineralised hard parts, most marine invertebrates produce metastable aragonite rather than the stable polymorph of CaCO3, calcite. After death of the organism the physiological conditions, which were present during biomineralisation, are not sustained any further and the system moves toward inorganic equilibrium with the surrounding inorganic geological system. Thus, during diagenesis the original biogenic structure of aragonitic tissue disappears and is replaced by inorganic structural features

Correlation gap in the optical spectra of the two-dimensional organic metal (BEDT-TTF)_4[Ni(dto)_2]

Optical reflection measurements within the highly conducting (a,b)-plane of the organic metal (BEDT-TTF)_4[Ni(dto)_2] reveal the gradual development of a sharp feature at around 200 cm as the temperature is reduced below 150 K. Below this frequency a narrow Drude-like response is observed which accounts for the metallic behavior. Since de Haas-von Alphen oscillations at low temperatures confirm band structure calculations of bands crossing the Fermi energy, we assign the observed behavior to a two-dimensional metallic state in the proximity of a correlation induced metal-insulator transition.Comment: 4 pages, 2 figure

Electronic correlation in the infrared optical properties of the quasi two dimensional κ\kappa-type BEDT-TTF dimer system

The polarized optical reflectance spectra of the quasi two dimensional organic correlated electron system $\kappa$-(BEDT-TTF)$_{2}$Cu[N(CN)$_{2}$]$Y$, $Y =$ Br and Cl are measured in the infrared region. The former shows the superconductivity at $T_{\rm c} \simeq$ 11.6 K and the latter does the antiferromagnetic insulator transition at $T_{\rm N} \simeq$ 28 K. Both the specific molecular vibration mode $\nu_{3}(a_{g})$ of the BEDT-TTF molecule and the optical conductivity hump in the mid-infrared region change correlatively at $T^{*} \simeq$ 38 K of $\kappa$-(BEDT-TTF)$_{2}$Cu[N(CN)$_{2}$]Br, although no indication of $T^{*}$ but the insulating behaviour below $T_{\rm ins} \simeq$ 50-60 K are found in $\kappa$-(BEDT-TTF)$_{2}$Cu[N(CN)$_{2}$]Cl. The results suggest that the electron-molecular vibration coupling on the $\nu_{3}(a_{g})$ mode becomes weak due to the enhancement of the itinerant nature of the carriers on the dimer of the BEDT-TTF molecules below $T^{*}$, while it does strong below $T_{\rm ins}$ because of the localized carriers on the dimer. These changes are in agreement with the reduction and the enhancement of the mid-infrared conductivity hump below $T^{*}$ and $T_{\rm ins}$, respectively, which originates from the transitions between the upper and lower Mott-Hubbard bands. The present observations demonstrate that two different metallic states of $\kappa$-(BEDT-TTF)$_{2}$Cu[N(CN)$_{2}$]Br are regarded as {\it a correlated good metal} below $T^{*}$ including the superconducting state and {\it a half filling bad metal} above $T^{*}$. In contrast the insulating state of $\kappa$-(BEDT-TTF)$_{2}$Cu[N(CN)$_{2}$]Cl below $T_{\rm ins}$ is the Mott insulator.Comment: 8 pages, 7 figure

Dissolved noble gases and stable isotopes as tracers of preferential fluid flow along faults in the Lower Rhine Embayment, Germany

Groundwater in shallow unconsolidated sedimentary aquifers close to the Bornheim fault in the Lower Rhine Embayment (LRE), Germany, has relatively low δ2H and δ18O values in comparison to regional modern groundwater recharge, and 4He concentrations up to 1.7 × 10−4 cm3 (STP) g–1 ± 2.2 % which is approximately four orders of magnitude higher than expected due to solubility equilibrium with the atmosphere. Groundwater age dating based on estimated in situ production and terrigenic flux of helium provides a groundwater residence time of ∼107 years. Although fluid exchange between the deep basal aquifer system and the upper aquifer layers is generally impeded by confining clay layers and lignite, this study’s geochemical data suggest, for the first time, that deep circulating fluids penetrate shallow aquifers in the locality of fault zones, implying  that sub-vertical fluid flow occurs along faults in the LRE. However, large hydraulic-head gradients observed across many faults suggest that they act as barriers to lateral groundwater flow. Therefore, the geochemical data reported here also substantiate a conduit-barrier model of fault-zone hydrogeology in unconsolidated sedimentary deposits, as well as corroborating the concept that faults in unconsolidated aquifer systems can act as loci for hydraulic connectivity between deep and shallow aquifers. The implications of fluid flow along faults in sedimentary basins worldwide are far reaching and of particular concern for carbon capture and storage (CCS) programmes, impacts of deep shale gas recovery for shallow groundwater aquifers, and nuclear waste storage sites where fault zones could act as potential leakage pathways for hazardous fluids