Constraints on the preservation of proxy data in carbonate archives – lessons from a marine limestone to marble transect, Latemar, Italy

This work evaluates an exceptionally complex natural laboratory, the Middle Triassic Latemar isolated platform in the northern Italian Dolomite Mountains and explores spatial and temporal gradients in processes and products related to contact metamorphism, dolomitization and dedolomitization of marine limestones. The relation between petrographic change and re-equilibration of geochemical proxy data is evaluated from the perspective of carbonate-archive research. Hydrothermal dolomitization of the limestone units is triggered by dykes and associated hydrothermal fluids radiating from the nearby Predazzo Intrusion. Detailed petrography, fluid inclusion analysis, δ13C and δ18O data and 87Sr/86Sr isotope ratios shed light on the extreme textural and geochemical complexity. Metamorphic and diagenetic patterns include: (i) peak-metamorphic and retrograde-metamorphic phases including three dolomite marbles, two dedolomite marbles, brucite, magnesium silicates and late-stage meteoric/vadose cement at the contact aureole; (ii) four spatially defined episodes of dolomitization, authigenic quartz, low magnesium calcite and late-stage meteoric cement at the Latemar isolated platform; and (iii) kilometre-scale gradients in δ13C values from the contact aureole towards the platform interior. Results shown here are relevant for two reasons: first, the spatial analysis of alteration products ranging from high-grade metamorphic overprint of marbles at temperatures of 700˚C in the contact aureole to moderately altered limestones in the platform interior at temperatures 20 km. Second, under rock-buffered conditions, and irrespective of metamorphic to diagenetic fluid-rock interactions, both marbles, and low-temperature hydrothermal dolomites have conservative marine δ13C and δ18O values. The fact that metamorphism and hydrothermal dolomitization of precursor limestones and early diagenetic dolostones did not per se reset environmental proxy data is of interest for those concerned with carbonate archive research in Earth’s deep time

Microborings reveal alternating agitation, resting and sleeping stages of modern marine ooids

ABSTRACTOoids are abundant carbonate grains throughout much of Earth's history, but their formation is not well understood. Here, an in‐depth study of microbial bioerosion features of Holocene ooids from the Schooner Cays ooid shoals (Great Bahama Bank, Eleuthera, Bahamas) and the Shalil al Ud ooid shoals in the Gulf (Abu Dhabi, United Arab Emirates) is presented. No obvious differences were found in ooid size distribution, cortex layer thickness, the composition of nuclei or euendolithic community when comparing ooids from both locations. Microendolithic borings are present in most studied ooid surfaces, but the intensity of (micro‐)bioerosion varies significantly. Applying an epoxy vacuum cast‐embedding technique allowed the identification of ichnotaxa and their inferred producers (various genera of diatoms, cyanobacteria, coccolithophores and unspecified bacteria). Euendolithic taxa have specific low‐light tolerances and light optima. This implies that information about the relative bathymetry (seafloor versus burial within an ooid shoal) and ecology for ooid cortex formation can be obtained via the presence or absence of their respective ichnotaxa. The history of a statistically significant number of ooid cortices can be translated into dune dynamics and the temporal variations thereof by allocating the inferred index producer to a defined burial or light penetration zone. In this context, ooid formation can be divided into four stages: (i) an agitation stage in the water column, characterized by the colonization of grains by photoautotrophs; (ii) a resting stage, characterized by temporary burial of the ooid, leading to immobilization and a shift towards heterotrophs; (iii) a sleeping stage, characterized by prolonged burial and colonialization by organotrophs; and (iv) a reactivation stage, characterized by a resurfacing of the ooid and a subsequent shift towards photoautotrophs. The sleeping stage is presumably a stage of ooid degradation where bioerosion, mainly by heterotrophic fungi and bacteria is particularly active.</jats:p

Microbial activity affects sulphur in biogenic aragonite

Carbonates that exhibit obvious diagenetic alteration are usually excluded as archives in palaeoenvironmental studies. However, the potential impact of microbial alteration during early diagenesis is still poorly explored. To investigate the sensitivity of sulphur concentration, distribution, oxidation state and isotopic composition in marine aragonite to microbial alteration, Arctica islandica bivalves and Porites sp. corals were experimentally exposed to anaerobic microbial activity. The anoxic incubation media included a benthic bacterial strain Shewanella sediminis and a natural anoxic sediment slurry with a natural microbial community of unknown species. Combined fluorescence microscopy and synchrotron‐based analysis of the sulphur distribution and oxidation state enabled a comparison of organic matter and sulphur content in the two materials. Results revealed a higher proportion of reduced sulphur species and locally stronger fluorescence within the pristine bivalve shell compared to the pristine coral skeleton. Within the pristine bivalve specimen, reduced sulphur was enriched in layers along the inner shell margin. After incubation in the anoxic sediment slurry, this region revealed rust‐brown staining and a patchy S2‐ distribution pattern rather than S2‐‐layers. Another effect on sulphur distribution was rust‐brown coloured fibres along one growth line, revealing a locally higher proportion of sulphur. The δ34S value of carbonate‐associated sulphate remained largely unaffected by both incubation media, but a lower δ34S value of water‐soluble sulphate reflected the degradation of insoluble organic matter by microbes in both experiments. No significant alteration was detected in the coral samples exposed to microbial alteration. The data clearly identified a distinct sensitivity of organically bound sulphur in biogenic aragonite to microbial alteration even when “traditional” geochemical proxies such as δ18OCARB or δ13CCARB in the carbonate didn’t show any effect. Differences in the intensity of microbial alteration documented are likely due to inherent variations in the concentration and nature of original organic compositions in the samples

Testing the preservation potential of early diagenetic dolomites as geochemical archives

Early marine diagenetic dolomite is a rather thermodynamically‐stable carbonate phase and has potential to act as an archive of marine porewater properties. However, the variety of early to late diagenetic dolomite phases that can coexist within a single sample can result in extensive complexity. Here, the archive potential of early marine dolomites exposed to extreme post‐depositional processes is tested using various types of analyses, including: petrography, fluid inclusion data, stable δ13C and δ18O isotopes, 87Sr/86Sr ratios, and U‐Pb age dating of various dolomite phases. In this example, a Triassic carbonate platform was dissected and overprinted (diagenetic temperatures of 50 to 430°C) in a strike‐slip zone in Southern Spain. Eight episodes of dolomitization, a dolostone cataclasite and late stage meteoric/vadose cementation were recognized. The following processes were found to be diagenetically relevant: (i) protolith deposition and fabric‐preservation, and marine dolomitization of precursor aragonite and calcite during the Middle–Late Triassic; (ii) intermediate burial and formation of zebra saddle dolomite and precipitation of various dolomite cements in a Proto‐Atlantic opening stress regime (T ca 250°C) during the Early–Middle Jurassic; (iii) dolomite cement precipitation during early Alpine tectonism, rapid burial to ca 15 km, and high‐grade anchizone overprint during Alpine tectonic evolution in the Early Eocene to Early Miocene; (iv) brecciation of dolostones to cataclasite during the onset of the Carboneras Fault Zone activity during the Middle Miocene; and (v) late‐stage regression and subsequent meteoric overprint. Data shown here document that, under favourable conditions, early diagenetic marine dolomites and their archive data may resist petrographic and geochemical resetting over time intervals of 108 or more years. Evidence for this preservation includes preserved Late Triassic seawater δ13CDIC values and primary fluid inclusion data. Data also indicate that oversimplified statements based on bulk data from other petrographically‐complex dolomite archives must be considered with caution

Deposition and Diagenesis of Subtropical Microbial Carbonates

The primary objective of this dissertation is to characterize freshwater microbial palustrine deposits, and assess how their textures and geochemical characteristics change over various stages of early burial and diagenesis in order to assess their recognition and preservation in the geologic record. A detailed study of sediments, microbial communities, and chemical environments was carried out for a sequence of cored Holocene deposits, from the modern surficial freshwater environment and seaward to those similar sediments buried during the Holocene transgression in the Florida Everglades (mainly terrestrial) and Florida Bay (full marine). In addition, the early diagenesis of microbial lime mud is also included as part of this dissertation to compare and contrast the diversity of microbial sediments and their diagenesis

Abiogenic aragonite crystal habit – Novel archive of precipitation environment?

Marine calcite cement's crystal habit is often considered a function of the fluid Mg/Ca ratio. In contrast, marine aragonite fabrics are commonly described as acicular (needle) cement with pointed terminations and width-to-length ratios in the order of 1:10. Similarly, botryoidal or spherulitic aragonite cements are well-known from Mesozoic (and older) reefal and slope depositional environments but are less common in Recent depositional environments. Here, we explore a wide range of abiogenic aragonite cement habits (morphologies) in caves and coastal marine depositional environments. We propose that the cement habit represents a novel (and underexplored) archive of diagenetic environment, fluid chemistry and precipitation kinetics. Based on SEM imaging, we find the often-described acicular and fibrous fabrics but also a plethora of less well-known morphotypes such as columnar (often pseudo-hexagonal prisms) and lath, tabular and sheet-like (prismatic single crystals) forms. Twinning of (flat) needle aragonite is observed and might point to precursor phases. Based on the data available, the common needle-type aragonite cement typifies normal marine diagenetic (porewater) environments. Increasingly complex habits (polysynthetic twins, flat needles, pseudo-prismatic and prismatic sheet-like) aragonite crystals) are present under increasing levels of restriction and precipitate from high-salinity porewaters. Intriguingly, pseudo-prismatic aragonite crystals are also present in meteoric, gravity-defying cave carbonates, specifically helictites. Aragonite cement habits are documented and placed into context with their depositional and diagenetic environment, and preliminary interpretations are presented

Constraints on the preservation of proxy data in carbonate archives – lessons from a marine limestone to marble transect, Latemar, Italy

Funding: This study was performed in the context of thecollaborative research initiative CHARON PhaseII (DFG Forschergruppe 1644). Open Access funding enabled and organized byProjekt DEAL.This work evaluates an exceptionally complex natural laboratory, the Middle Triassic Latemar isolated platform in the northern Italian Dolomite Mountains and explores spatial and temporal gradients in processes and products related to contact metamorphism, dolomitization and dedolomitization of marine limestones. The relation between petrographic change and re-equilibration of geochemical proxy data is evaluated from the perspective of carbonate-archive research. Hydrothermal dolomitization of the limestone units is triggered by dykes and associated hydrothermal fluids radiating from the nearby Predazzo Intrusion. Detailed petrography, fluid inclusion analysis, δ13C and δ18O data and 87Sr/86Sr isotope ratios shed light on the extreme textural and geochemical complexity. Metamorphic and diagenetic patterns include: (i) peak-metamorphic and retrograde-metamorphic phases including three dolomite marbles, two dedolomite marbles, brucite, magnesium silicates and late-stage meteoric/vadose cement at the contact aureole; (ii) four spatially defined episodes of dolomitization, authigenic quartz, low magnesium calcite and late-stage meteoric cement at the Latemar isolated platform; and (iii) kilometre-scale gradients in δ13C values from the contact aureole towards the platform interior. Results shown here are relevant for two reasons: first, the spatial analysis of alteration products ranging from high-grade metamorphic overprint of marbles at temperatures of 700°C in the contact aureole to moderately altered limestones in the platform interior at temperatures 20 km. Second, under rock-buffered conditions, and irrespective of metamorphic to diagenetic fluid−rock interactions, both marbles, and low-temperature hydrothermal dolomites have conservative marine δ13C and δ18O values. The fact that metamorphism and hydrothermal dolomitization of precursor limestones and early diagenetic dolostones did not per se reset environmental proxy data is of interest for those concerned with carbonate archive research in Earth’s deep time.Publisher PDFPeer reviewe

Late Holocene to recent aragonite-cemented transgressive lag deposits in the Abu Dhabi lagoon and intertidal sabkha

Modern cemented intervals (beachrock, firmgrounds to hardgrounds and concretionary layers) form in the lagoon and intertidal sabkha of Abu Dhabi. Seafloor lithification actively occurs in open, current-swept channels in low-lying areas between ooid shoals, in the intertidal zone of the middle lagoon, some centimetres beneath the inner lagoonal seafloor (i.e. within the sediment column) and at the sediment surface the intertidal sabkha. The concept of "concretionary sub-hardgrounds", i.e. laminar cementation of sediments formed within the sediment column beneath the shallow redox boundary, is introduced and discussed. Based on calibrated radiocarbon ages, seafloor lithification commenced during the Middle to Late Holocene ($\it {ca}$ 9000 cal yr $\tiny {BP})$, and proceeds to the present-day. Lithification occurs in the context of the actualistic relative sea-level rise shifting the coastline landward across the extremely low-angle carbonate ramp. The cemented intervals are interpreted as parasequence boundaries in the sense of "marine flooding surfaces", but in most cases the sedimentary cover overlying the transgressive surface has not yet been deposited. Aragonite, (micritic) calcite and, less commonly, gypsum cements lithify the firmground/hardground intervals. Cements are described and placed into context with their depositional and marine diagenetic environments and characterized by means of scanning electron microscope petrography, cathodoluminescence microscopy and Raman spectroscopy. The morphology of aragonitic cements changes from needle-shaped forms in lithified decapod burrows of the outer lagoon ooidal shoals to complex columnar, lath and platy crystals in the inner lagoon. Precipitation experiments provide first tentative evidence for the parameters that induce changes in aragonite cement morphology. Data shown here shed light on ancient, formerly aragonite-cemented seafloors, now altered to diagenetic calcites, but also document the complexity of highly dynamic near coastal depositional environments