Middle Ordovician Upwelling-Related Ironstone of North Wales: Coated Grains, Ocean Chemistry, and Biological Evolution

Middle Ordovician phosphatic ironstone of the Welsh Basin provides new insight into the paleoenvironmental significance of ironstone and Ordovician ocean chemistry. Deposition occurred in a back-arc basin along the southern margin of Avalonia as the Rheic Ocean opened to the south. Ironstone is interpreted to have accumulated as part of an aggradational parasequence on a storm-dominated shelf with coastal upwelling. This parasequence has a laminated pyritic mudstone base that grades upward into variably bioturbated mudstone and coated grain-rich, intraclastic ironstone, which is overlain in turn by cross-stratified grainstone composed entirely of coated Fe grains. A coarser clastic parasequence composed of more proximal lithofacies rests conformably above and suggests the contact between the two parasequences is a maximum flooding surface marking the onset of highstand conditions. Lithofacies associations suggest that sustained coastal upwelling created a wedge of nutrient-rich, ferruginous seawater on the middle shelf that stimulated high surface ocean productivities. Large, coated Fe grains (granule size) composed of discontinuous and concentric carbonate fluorapatite, hematite, and chamosite cortical layers record fluctuations in pore water Eh that are interpreted to have been related to changes in upwelling intensity and intermittent storm reworking of the seafloor. Results support an emerging model for Ordovician ironstone underpinned by the development of ferruginous bottom water that was periodically tapped by coastal upwelling. Expanding, semi-restricted seaways such as the Rheic Ocean were ideal locations for the ponding of this anoxic, hydrothermally enriched seawater, especially during the early Paleozoic when the deep ocean was variably and inconsistently oxygenated. The coincidence of ironstone depositional episodes with graptolite diversification events suggests that, in addition to Fe, the sustained supply of upwelling-related P may have driven the radiation of some planktonic ecosystems during the Great Ordovician Biodiversification Event. Concomitant minor extinctions of benthic trilobites occurred as these ferruginous waters impinged on the shelf.

X-ray nanotomography and electron backscatter diffraction demonstrate the crystalline, heterogeneous and impermeable nature of conodont white matter

Conodont elements, microfossil remains of extinct primitive vertebrates, are commonly exploited as mineral archives of ocean chemistry, yielding fundamental insights into the palaeotemperature and chemical composition of past oceans. Geochemical assays have been traditionally focused on the so-called lamellar and white matter crown tissues; however, the porosity and crystallographic nature of the white matter and its inferred permeability are disputed, raising concerns over its suitability as a geochemical archive. Here, we constrain the characteristics of this tissue and address conflicting interpretations using ptychographic X-ray-computed tomography (PXCT), pore network analysis, synchrotron radiation X-ray tomographic microscopy (srXTM) and electron back-scatter diffraction (EBSD). PXCT and pore network analyses based on these data reveal that while white matter is extremely porous, the pores are unconnected, rendering this tissue closed to postmortem fluid percolation. EBSD analyses demonstrate that white matter is crystalline and comprised of a single crystal typically tens of micrometres in dimensions. Combined with evidence that conodont elements grow episodically, these data suggest that white matter, which comprises the denticles of conodont elements, grows syntactically, indicating that individual crystals are time heterogeneous. Together these data provide support for the interpretation of conodont white matter as a closed geochemical system and, therefore, its utility of the conodont fossil record as a historical archive of Palaeozoic and Early Mesozoic ocean chemistry.

The impacts of past, present and future ocean chemistry on predatory planktonic snails

The atlantid heteropods represent the only predatory, aragonite shelled zooplankton. Atlantid shell production is likely to be sensitive to ocean acidification (OA), and yet we know little about their mechanisms of calcification, or their response to changing ocean chemistry. Here, we present the first study into calcification and gene expression effects of short-term OA exposure on juvenile atlantids across three pH scenarios: mid-1960s, ambient and 2050 conditions. Calcification and gene expression indicate a distinct response to each treatment. Shell extension and shell volume were reduced from the mid-1960s to ambient conditions, suggesting that calcification is already limited in today's South Atlantic. However, shell extension increased from ambient to 2050 conditions. Genes involved in protein synthesis were consistently upregulated, whereas genes involved in organismal development were downregulated with decreasing pH. Biomineralization genes were upregulated in the mid-1960s and 2050 conditions, suggesting that any deviation from ambient carbonate chemistry causes stress, resulting in rapid shell growth. We conclude that atlantid calcification is likely to be negatively affected by future OA. However, we also found that plentiful food increased shell extension and shell thickness, and so synergistic factors are likely to impact the resilience of atlantids in an acidifying ocean.

Isotopically “heavy” pyrite in marine sediments due to high sedimentation rates and non-steady-state deposition

Sedimentary pyrite formation links the global biogeochemical cycles of carbon, sulfur, and iron, which, in turn, modulate the redox state of the planet’s surficial environment over geological time scales. Accordingly, the sulfur isotopic composition (δ34S) of pyrite has been widely employed as a geochemical tool to probe the evolution of ocean chemistry. Characteristics of the depositional environment and post-depositional processes, however, can modify the δ34S signal that is captured in sedimentary pyrite and ultimately preserved in the geological record. Exploring sulfur and iron diagenesis within the Bornholm Basin, Baltic Sea, we find that higher sedimentation rates limit the near-surface sulfidization of reactive iron, facilitating its burial and hence the subsurface availability of reactive iron for continued and progressively more 34S-enriched sediment-hosted pyrite formation (δ34S ≈ –5‰). Using a diagenetic model, we show that the amount of pyrite formed at the sediment-water interface has increased over the past few centuries in response to expansion of water-column hypoxia, which also impacts the sulfur isotopic signature of pyrite at depth. This contribution highlights the critical role of reactive iron in pyrite formation and questions to what degree pyrite δ34S values truly reflect past global ocean chemistry and biogeochemical processes. This work strengthens our ability to extract local paleoenvironmental information from pyrite δ34S signatures.

Production and calcification variations of the key coccolithophore species Gephyrocapsa during the Late Pleistocene (MIS 14 to MIS 7)

<p>There is an increasing interest in understanding the role of coccolithophores, a group of major calcifying phytoplankton, in the marine carbon cycle: they have a dual contribution to the operation of the carbonate and biological pumps during their lifecycle. How the recent changes in seawater carbonate chemistry are affecting their production and calcification is a matter of debate in the scientific community. Culture experiments suggest that modern coccolithophore species (<em>Emiliania huxleyi</em>) is sensitive to such variations. Conversely, could past evolutionary or adaptative changes in the most important coccolithophore species have an impact on ocean chemistry?  </p><p>We focus on the interval comprising the MIS 14 to 7 (Mid-Brunhes, Pleistocene) when a remarkable increase in the amplitude of glacial/interglacial atmospheric CO<sub>2</sub> was recorded. We analyzed (i) the composition of the dominant coccolithophore <em>Gephyrocapsa</em> assemblages and (ii) the morphometric parameters (length, mass, and thickness) of its coccoliths (carbonated scales) <span>in samples from a set of sediment cores (Sites IODP U1314, U1385and ODP 925 and 977) located in a north-south transect in the North Atlantic and the western Mediterranean Sea. We estimated the primary productivity conditions at the different regions and explore methodological approaches to measure the calcification of <em>Gephyrocapsa</em> coccoliths.</span></p><p>Preliminary results show a correlation between the abundance of coccoliths, assemblage composition, and coccolith morphology at different regions. A comparison with geochemical and sedimentological records suggests a significant role of <em>Gephyrocapsa</em> coccolithophore in marine organic and carbonate production throughout the interval. These observations open the discussion about the existence of a global environmental relationship between coccolithophore assemblages and coccolith morphometrical variations, but also, a possible impact of the changes in the <em>Gephyrocapsa</em> production and calcification on the ocean chemistry.</p>