Beschreibung: Ocean environmental conditions can be inferred from the chemical composition of bamboo coral skeletons. The high magnesium calcite internodes of these long-living octocorals may therefore represent a potential archive for seawater properties such as salinity or temperature where instrumental time series are absent. To extend these time series into the past using a natural archive the principles of temperature and salinity signal incorporation into cold-water coral skeletal material need to be investigated. Since skeletal Na and S concentrations have been proposed as environmental proxies, we mapped the spatial distribution and concentration of these elements in two Atlantic specimens of Keratoisis grayi (family Isididae). These measurements were conducted with an electron microprobe applying a spatial resolution of 4 μm. The mean apparent distribution coefficient of Na/Ca for the two samples was within 2.5 and 2.8*10−4, while that of S shows a similar depletion relative to seawater with 3.8 and 3.6*10−3. The two elements show an inverse correlation in bamboo coral skeletons. The mean apparent distribution coefficient of Na is similar to that of abiotic calcites. This similarity can be interpreted as the absence of significant vital effects for skeletal Na/Ca. Hence it corroborates the idea that the average skeletal composition of bamboo corals holds the potential to record past seawater conditions. In contrast, it appears unlikely that the spatial variations of the element distribution of seemingly simultaneously precipitated material along growth rings are exclusively controlled by environmental factors. We further exclude Rayleigh fractionation, ion-specific pumping, and Ca/proton exchange as the driver of Na and S distribution in bamboo corals. Instead, we adapt a calcification model originally proposed for scleractinians to bamboo corals. This model can explain the observed distribution of Na and S in the skeleton by a combination of Ca/proton pumping, bicarbonate active transport, and the formation of an organic skeletal matrix. The adapted model can further be used to predict the theoretical behaviour of other elements and disentangle vital effects from external factors influencing compositional features. It is therefore a useful tool for future studies on the potential of bamboo corals as environmental archives.

Beschreibung: During Earth’s history, precipitation of calcium carbonate by heterotrophic microbes has substantially contributed to the genesis of copious amounts of carbonate sediment and its subsequent lithification. Previous work identified the microbial sulfur and nitrogen cycle as principal pathways involved in the formation of marine calcium carbonate deposits. While substantial knowledge exists for the importance of the sulfur cycle, specifically sulfate reduction, with regard to carbonate formation, information about carbonate genesis connected to the microbial nitrogen cycle is dissatisfactory. In addition to the established pathways for carbonate mineral formation, also the potential of microbial carbonic anhydrase, a carbonate-relevant, zinc-containing enzyme, is receiving currently increased attention. However, also in this field knowledge is scarce and fragmentary. Here we demonstrate microbial carbonate precipitation as a direct result of the interplay between the microbial nitrogen cycle and a microbially produced enzyme. Using Alcanivorax borkumensis as a model organism, our experiments depict precipitation of a peloidal carbonate matrix within days to weeks, induced by simultaneous ammonification and extracellular carbonic anhydrase activity. The precipitates show similar morphology, mineralogy, δ44/40Ca, and δ88/86Sr to analogs of modern carbonate peloids. The obtained Sr/Ca partition coefficient DSr showed no clear deviation from inorganic carbonate phases, indicating that microbially mediated carbonate precipitation, indeed, follows the principles of physico-chemical precipitation. The observed relative enrichment of the precipitates in zinc might help to constrain zinc variations in natural carbonate archives. Our study demonstrates that ammonification, due to intense microbial organic matter degradation, and carbonic anhydrase may play a substantial role for calcium carbonate precipitation in paleo- and recent shallow marine environments.

Beschreibung: The geological calcium cycle is linked to the geological carbon cycle through the weathering and burial of carbonate rocks. As a result, calcium (Ca) isotope ratios (44Ca/40Ca, expressed as δ44/40Ca) can help to constrain ancient carbon cycle dynamics if Ca cycle behavior can be reconstructed. However, the δ44/40Ca of carbonate rocks is influenced not only by the δ44/40Ca of seawater but also by diagenetic processes and fractionation associated with carbonate precipitation. In this study, we investigate the dominant controls on carbonate δ44/40Ca in Upper Permian to Middle Triassic limestones (ca. 253 to 244 Ma) from south China and Turkey. This time interval is ideal for assessing controls on Ca isotope ratios in carbonate rocks because fluctuations in seawater δ44/40Ca may be expected based on several large carbon isotope (δ13C) excursions ranging from − 2 to + 8‰. Parallel negative δ13C and δ44/40Ca excursions were previously identified across the end-Permian extinction horizon. Here, we find a second negative excursion in δ44/40Ca of ~ 0.2‰ within Lower Triassic strata in both south China and Turkey; however, this excursion is not synchronous between regions and thus cannot be interpreted to reflect secular change in the δ44/40Ca of global seawater. Additionally, δ44/40Ca values from Turkey are consistently 0.3‰ lower than contemporaneous samples from south China, providing further support for local or regional influences. By measuring δ44/40Ca and Sr concentrations ([Sr]) in two stratigraphic sections located at opposite margins of the Paleo-Tethys Ocean, we can determine whether the data represent global conditions (e.g., secular variations in the δ44/40Ca of seawater) versus local controls (e.g., original mineralogy or diagenetic alteration). The [Sr] and δ44/40Ca data from this study are best described statistically by a log-linear correlation that also exists in many previously published datasets of various geological ages. Using a model of early marine diagenetic water-rock interaction, we illustrate that this general correlation can be explained by the chemical evolution of bulk carbonate sediment samples with different initial mineralogical compositions that subsequently underwent recrystallization. Although early diagenetic resetting and carbonate mineralogy strongly influence the carbonate δ44/40Ca values, the relationship between [Sr] and δ44/40Ca holds potential for reconstructing first-order secular changes in seawater δ44/40Ca composition.

Beschreibung: Coccoliths comprise a major fraction of the global carbonate sink. Therefore, changes in coccolithophores' Ca isotopic fractionation could affect seawater Ca isotopic composition, affecting interpretations of the global Ca cycle and related changes in seawater chemistry and climate. Despite this, a quantitative interpretation of coccolith Ca isotopic fractionation and a clear understanding of the mechanisms driving it are not yet available. Here, we address this gap in knowledge by developing a simple model (CaSri–Co) to track coccolith Ca isotopic fractionation during cellular Ca uptake and allocation to calcification. We then apply it to published and new δ44/40Ca and Sr/Ca data of cultured coccolithophores of the species Emiliania huxleyi and Gephyrocapsa oceanica. We identify changes in calcification rates, Ca retention efficiency and solvation–desolvation rates as major drivers of the Ca isotopic fractionation and Sr/Ca variations observed in cultures. Higher calcification rates, higher Ca retention efficiencies and lower solvation–desolvation rates increase both coccolith Ca isotopic fractionation and Sr/Ca. Coccolith Ca isotopic fractionation is most sensitive to changes in solvation–desolvation rates. Changes in Ca retention efficiency may be a major driver of coccolith Sr/Ca variations in cultures. We suggest that substantial changes in the water structure strength caused by past changes in temperature could have induced significant changes in coccolithophores' Ca isotopic fractionation, potentially having some influence on seawater Ca isotopic composition. We also suggest a potential effect on Ca isotopic fractionation via modification of the solvation environment through cellular exudates, a hypothesis that remains to be tested.

Beschreibung: Highlights • First systematic description of Pleistocene facies of the Maldives reveals shallow-water deposits • Only U-series ages from Pleistocene deposits of the Maldives (MIS 5e) • Geochronology and paleo-bathymetric analyses allow estimation of late Quaternary subsidence of this major carbonate platform location to 0.09 - 0.16 m/kyr To date, there is hardly any knowledge of facies and age of Pleistocene reef limestone in the Maldives. Likewise, there are no robust estimates of Quaternary subsidence in this major shallow-water carbonate platform and reef area. In a core recovered on the windward margin of Rasdhoo Atoll in the central part of the archipelago, Pleistocene coralgal grainstone facies belonging to marine isotope stage (MIS) 5e were recovered underlying a Holocene reef succession, 14.5 m below modern sea level. Based on the occurrence of shallow-water stony corals such as Isopora palifera and possibly Acropora gr. robusta, high-energy coralline algae including Porolithon onkodes, in part associated with vermetids, and grain-supported limestone texture, the paleoenvironment is interpreted as a shallow back reef area with a paleo-waterdepth of 〈10 m. Based on a reliable U-series age from a Pleistocene acroporid coral of 136.9 kyr BP and assuming a + 7.5 m higher-than-present peak sea level during MIS 5e, late Quaternary subsidence is estimated to 0.09 m/kyr (minimum)–0.16 m/kyr (maximum value). A sea level of +2.5 m during the early MIS 5e would reduce the rates to 0.05 m/kyr (minimum)–0.12 m/kyr (maximum). These numbers are significant for reconstructions of depositional environments of this major carbonate platform area in the Quaternary. The subsidence estimates are not as crucial for historical reconstruction of relative sea level and for predictions of the near future in this low-lying archipelago, because they will add only a minor portion to the predicted rates of 21st century sea-level rise.

Beschreibung: Fossil carbonate skeletons of marine organisms are archives for understanding the development and evolution of palaeo-environments. However, the correct assessment of past environment dynamics is only possible when pristine skeletons and their biogenic characteristics are unequivocally distinguishable from diagenetically-altered skeletal elements and non-biogenic features. In this study, we extend our work on diagenesis of biogenic aragonite (Casella et al. 2017) to the investigation of biogenic low-Mg calcite using brachiopod shells. We examined and compared microstructural characteristics induced by laboratory-based alteration to structural features derived from diagenetic alteration in natural environments. We used four screening methods: cathodoluminescence (CL), cryogenic and conventional field emission-scanning electron microscopy (FE-SEM), atomic force microscopy (AFM) and electron backscatter diffraction (EBSD). We base our assessments of diagenetic alteration and overprint on measurements of, a) images of optical overprint signals, b) changes in calcite crystal orientation patterns, and c) crystal co-orientation statistics. According to the screening process, altered and overprinted samples define two groups. In Group 1 the entire shell is diagenetically overprinted, whereas in Group 2 the shell contains pristine as well as overprinted parts. In the case of Group 2 shells, alteration occurred either along the periphery of the shell including the primary layer or at the interior-facing surface of the fibrous/columnar layer. In addition, we observed an important mode of the overprinting process, namely the migration of diagenetic fluids through the endopunctae corroborated by mineral formation and overprinting in their immediate vicinity, while leaving shell parts between endopunctae in pristine condition. Luminescence (CL) and microstructural imaging (FE-SEM) screening give first-order observations of the degree of overprint as they cover macro-to micron scale alteration features. For a comprehensive assessment of diagenetic overprint these screening methods should be complemented by screening techniques such as EBSD and AFM. They visualise diagenetic changes at submicron and nanoscale levels depicting the replacement of pristine nanocomposite mesocrystal biocarbonate (NMB) by inorganic rhombohedral calcite (IRC). The integration of screening methods allows for the unequivocal identification of highly-detailed alteration features as well as an assessment of the degree of diagenetic alteration.

Beschreibung: The assessment of diagenetic overprint on microstructural and geochemical data gained from fossil archives is of fundamental importance for understanding palaeoenvironments. The correct reconstruction of past environmental dynamics is only possible when pristine skeletons are unequivocally distinguished from altered skeletal elements. Our previous studies show (i) that replacement of biogenic carbonate by inorganic calcite occurs via an interface-coupled dissolution–reprecipitation mechanism. (ii) A comprehensive understanding of alteration of the biogenic skeleton is only given when structural changes are assessed on both, the micrometre as well as on the nanometre scale. In the present contribution we investigate experimental hydrothermal alteration of six different modern biogenic carbonate materials to (i) assess their potential for withstanding diagenetic overprint and to (ii) find characteristics for the preservation of their microstructure in the fossil record. Experiments were performed at 175°C with a 100 mM NaCl + 10 mM MgCl2 alteration solution and lasted for up to 35 days. For each type of microstructure we (i) examine the evolution of biogenic carbonate replacement by inorganic calcite, (ii) highlight different stages of inorganic carbonate formation, (iii) explore microstructural changes at different degrees of alteration, and (iv) perform a statistical evaluation of microstructural data to highlight changes in crystallite size between the pristine and the altered skeletons. We find that alteration from biogenic aragonite to inorganic calcite proceeds along pathways where the fluid enters the material. It is fastest in hard tissues with an existing primary porosity and a biopolymer fabric within the skeleton that consists of a network of fibrils. The slowest alteration kinetics occurs when biogenic nacreous aragonite is replaced by inorganic calcite, irrespective of the mode of assembly of nacre tablets. For all investigated biogenic carbonates we distinguish the following intermediate stages of alteration: (i) decomposition of biopolymers and the associated formation of secondary porosity, (ii) homoepitactic overgrowth with preservation of the original phase leading to amalgamation of neighbouring mineral units (i.e. recrystallization by grain growth eliminating grain boundaries), (iii) deletion of the original microstructure, however, at first, under retention of the original mineralogical phase, and (iv) replacement of both, the pristine microstructure and original phase with the newly formed abiogenic product. At the alteration front we find between newly formed calcite and reworked biogenic aragonite the formation of metastable Mg-rich carbonates with a calcite-type structure and compositions ranging from dolomitic to about 80mol % magnesite. This high-Mg calcite seam shifts with the alteration front when the latter is displaced within the unaltered biogenic aragonite. For all investigated biocarbonate hard tissues we observe the destruction of the microstructure first, and, in a second step, the replacement of the original with the newly formed phase.