Assessment of hydrothermal alteration on micro- and nanostructures of biocarbonates: quantitative statistical grain-area analysis of diagenetic overprint

Abstract. The assessment of diagenetic overprint on microstructural and geochemical data gained from fossil archives is of fundamental importance for understanding palaeoenvironments. A correct reconstruction of past environmental dynamics is only possible when pristine skeletons are unequivocally distinguished from altered skeletal elements. Our previous studies (Casella et al., 2017) have shown that replacement of biogenic carbonate by inorganic calcite occurs via an interface coupled dissolution–reprecipitation mechanism. Furthermore, for a comprehensive assessment of alteration, structural changes have to be assessed on the nanoscale as well, which documents the replacement of pristine nanoparticulate calcite by diagenetic nanorhombohedral calcite (Casella et al., 2018a, b). In the present contribution we investigated six different modern biogenic carbonate microstructures for their behaviour under hydrothermal alteration in order to assess their potential to withstand diagenetic overprint and to test the integrity of their preservation in the fossil record. For each microstructure (a) the evolution of biogenic aragonite and calcite replacement by inorganic calcite was examined, (b) distinct carbonate mineral formation steps on the micrometre scale were highlighted, (c) microstructural changes at different stages of alteration were explored, and (d) statistical analysis of differences in basic mineral unit dimensions in pristine and altered skeletons was performed. The latter analysis enables an unequivocal determination of the degree of diagenetic overprint and discloses information especially about low degrees of hydrothermal alteration.

[1]  J. M. Astilleros,et al.  Epitactic Overgrowths of Calcite (CaCO3) on Anhydrite (CaSO4) Cleavage Surfaces , 2018 .

[2]  A. Niedermayr,et al.  Exploring the impact of diagenesis on (isotope) geochemical and microstructural alteration features in biogenic aragonite , 2017 .

[3]  A. Immenhauser,et al.  Experimental diagenesis: insights into aragonite to calcite transformation of Arctica islandica shells by hydrothermal treatment , 2016 .

[4]  J. Brugger,et al.  Textural and compositional complexities resulting from coupled dissolution–reprecipitation reactions in geomaterials , 2015 .

[5]  C. Korte,et al.  Diagenetic alteration in low-Mg calcite from macrofossils: a review , 2015 .

[6]  A. Putnis,et al.  Coupled dissolution and precipitation at mineral-fluid interfaces , 2014 .

[7]  J. Brugger,et al.  Grain boundaries as microreactors during reactive fluid flow: experimental dolomitization of a calcite marble , 2014, Contributions to Mineralogy and Petrology.

[8]  B. Schöne Arctica islandica (Bivalvia): A unique paleoenvironmental archive of the northern North Atlantic Ocean , 2013 .

[9]  B. Maier,et al.  Homoepitaxial meso- and microscale crystal co-orientation and organic matrix network structure in Mytilus edulis nacre and calcite. , 2013, Acta biomaterialia.

[10]  J. Scourse,et al.  The dog cockle, Glycymeris glycymeris (L.), a new annually-resolved sclerochronological archive for the Irish Sea , 2013 .

[11]  J. Czernuszka,et al.  Characterizing the microstructure of Arctica islandica shells using NanoSIMS and EBSD , 2012 .

[12]  Julyan H E Cartwright,et al.  Mineral bridges in nacre. , 2011, Journal of structural biology.

[13]  A. Putnis,et al.  Experimental study of the aragonite to calcite transition in aqueous solution , 2011 .

[14]  B. Morton The biology and functional morphology of Arctica islandica (Bivalvia: Arcticidae) – A gerontophilic living fossil , 2011 .

[15]  B. Schöne,et al.  Gulf of Maine shells reveal changes in seawater temperature seasonality during the Medieval Climate Anomaly and the Little Ice Age , 2011 .

[16]  Guorong Chen,et al.  Three-Dimensional Ordered Arrays of Zeolite Nanocrystals with Uniform Size and Orientation by a Pseudomorphic Coupled Dissolution−Reprecipitation Replacement Route , 2009 .

[17]  I. Harris,et al.  Accurate increment identification and the spatial extent of the common signal in five Arctica islandica chronologies from the Fladen Ground, northern North Sea , 2009 .

[18]  A. Putnis,et al.  Mechanism and kinetics of pseudomorphic mineral replacement reactions: A case study of the replacement of pentlandite by violarite , 2009 .

[19]  M. Willinger,et al.  The key role of the surface membrane in why gastropod nacre grows in towers , 2009, Proceedings of the National Academy of Sciences.

[20]  S. Weiner,et al.  Forming nacreous layer of the shells of the bivalves Atrina rigida and Pinctada margaritifera: an environmental- and cryo-scanning electron microscopy study. , 2008, Journal of structural biology.

[21]  D. Clague,et al.  Palaeoenvironmental records from fossil corals: The effects of submarine diagenesis on temperature and climate estimates , 2007 .

[22]  Christopher J. Johnson,et al.  Architecture of columnar nacre, and implications for its formation mechanism. , 2007, Physical review letters.

[23]  J. Cartwright,et al.  The dynamics of nacre self-assembly , 2007, Journal of The Royal Society Interface.

[24]  Xiaodong Li,et al.  In situ observation of nanograin rotation and deformation in nacre. , 2006, Nano letters.

[25]  T. Okamoto,et al.  Organization pattern of nacre in Pteriidae (Bivalvia: Mollusca) explained by crystal competition , 2006, Proceedings of the Royal Society B: Biological Sciences.

[26]  Steve Weiner,et al.  Mollusk Shell Formation: A Source of New Concepts for Understanding Biomineralization Processes , 2006 .

[27]  A. Fallick,et al.  Shell structure, patterns and trends of oxygen and carbon stable isotopes in modern brachiopod shells , 2005 .

[28]  T. Pohlmann,et al.  A seasonally resolved bottom‐water temperature record for the period AD 1866–2002 based on shells of Arctica islandica (Mollusca, North Sea) , 2005 .

[29]  P. Walther,et al.  Architecture of the organic matrix in the sternal CaCO3 deposits of Porcellio scaber (Crustacea, Isopoda). , 2005, Journal of structural biology.

[30]  Clément Sanchez,et al.  Biomimetism and bioinspiration as tools for the design of innovative materials and systems , 2005, Nature materials.

[31]  B. Schöne,et al.  Daily Growth Rates in Shells of Arctica islandica: Assessing Sub-seasonal Environmental Controls on a Long-lived Bivalve Mollusk , 2005 .

[32]  Frédéric Marin,et al.  Molluscan shell proteins , 2004 .

[33]  B. Schöne,et al.  Sea surface water temperatures over the period 1884–1983 reconstructed from oxygen isotope ratios of a bivalve mollusk shell (Arctica islandica, southern North Sea) , 2004 .

[34]  A. Logan,et al.  Geochemistry of modern brachiopods: applications and implications for oceanography and paleoceanography , 2003 .

[35]  P. deMenocal,et al.  Environmental controls on the stable isotopic composition of Mercenaria mercenaria: Potential application to paleoenvironmental studies , 2003 .

[36]  E. Bard,et al.  New TIMS constraints on the uranium-238 and uranium-234 in seawaters from the main ocean basins and the Mediterranean Sea , 2002 .

[37]  Zhigang Suo,et al.  Deformation mechanisms in nacre , 2001 .

[38]  R. Maliva,et al.  Skeletal aragonite neomorphism in Plio-Pleistocene sandy limestones and sandstones, Hollywood, Florida, USA , 2000 .

[39]  J. Marshall,et al.  Two-Stage Neomorphism of Jurassic Aragonitic Bivalves: Implications for Early Diagenesis , 1995 .

[40]  E. Grossman,et al.  Stable isotopes in Late Pennsylvanian brachiopods from the United States: Implications for Carboniferous paleoceanography , 1993 .

[41]  Arnold I. Miller,et al.  Production and Cycling of Calcium Carbonate in a Shelf-Edge Reef System (St. Croix, U.S. Virgin Islands): Applications to the Nature of Reef Systems in the Fossil Record , 1990 .

[42]  Niels-Henrik Schmidt,et al.  Computer-aided determination of crystal-lattice orientation from electron channeling patterns in the SEM , 1989 .

[43]  G. D. Martin,et al.  The role of skeletal porosity in aragonite neomorphism-Strombus and Montastrea from the Pleistocene Key Largo Limestone, Florida , 1986 .

[44]  J. Veizer,et al.  Chemical Diagenesis of a Multicomponent Carbonate System -2: Stable Isotopes , 1981 .

[45]  M. Z. Stout,et al.  Transformation of aragonite to calcite in a marine gasteropod , 1978 .

[46]  R. Bathurst Carbonate Sediments and Their Diagenesis , 1972 .

[47]  G. Friedman Early Diagenesis and Lithification in Carbonate Sediments , 1964 .

[48]  A. Immenhauser,et al.  Hydrothermal replacement of biogenic and abiogenic aragonite by Mg-carbonates – Relation between textural control on effective element fluxes and resulting carbonate phase , 2017 .

[49]  J. Morse,et al.  Formation and Diagenesis of Carbonate Sediments , 2014 .

[50]  A. Putnis Mineral Replacement Reactions , 2009 .

[51]  C. Richardson Molluscs as archives of environmental change. , 2001 .

[52]  Y. Dauphin,et al.  Mineralogy, chemistry and ultrastructure of the external shell-layer in ten species of Haliotis with reference to Haliotis tuberculata (Mollusca: Archaeogastropoda) , 1989 .