Zinc- and cadmium-isotope evidence for redox-driven perturbations to global micronutrient cycles during Oceanic Anoxic Event 2 (Late Cretaceous)

This study uses organic-rich sediments from the Tarfaya Basin, Morocco, to assess the Cd- and Zn-isotope response to dramatic global palaeoenvironmental change during the Cenomanian–Turonian interval (Late Cretaceous). These organic-rich continental-margin deposits include an expression of Oceanic Anoxic Event 2 (OAE 2, ∼94 Ma), an interval associated with the spread of low-oxygen marine environments and widespread burial of organic-rich sediments. Due to placement of the Tarfaya Basin in a region of upwelling and relatively constant local environmental conditions, the stratigraphic variations in δ114Cd and δ66Zn values largely reflect changes in the seawater isotopic composition of the sub-surface proto-North Atlantic Ocean. Positive shifts of ∼0.2–0.3‰ away from background values in δ114Cd and δ66Zn are observed during the main phase of the positive carbon-isotope excursion associated with OAE 2. These isotopic shifts are coeval with decreases in Cd/TOC and Zn/TOC ratios and thus imply that drawdown of isotopically light Cd and Zn from seawater inventories was a result of extensive burial of these metals in organic-rich marine sediments globally. Low δ66Zn values during the Plenus Cold Event, a cooler episode during OAE 2, are similar in timing and magnitude to variations found in the English Chalk (Eastbourne, UK) and support the inference of a global control on these isotopic excursions. The δ66Zn values during the Plenus Cold Event are taken to record global oxygenation, possibly including the remobilization of isotopically light Zn from continental-margin sediments. A considerably smaller change in δ114Cd values for this interval implies that the Cd- and Zn-isotope systems can provide information about slightly different environmental processes, with global seawater composition with respect to Zn also being influenced by the magnitude of oxic removal sinks and isotopically light Zn input fluxes from sediments and hydrothermal fluids

The influence of thermal maturity on the stable isotope compositions and concentrations of molybdenum, zinc and cadmium in organic-rich marine mudrocks

The concentrations and isotopic compositions of molybdenum (Mo), zinc (Zn) and cadmium (Cd) in organic-rich marine mudrocks may be used to characterize ocean chemistry in the geological past. These approaches rely on the rarely tested assumption that the geochemical signatures of these metals are not affected by the thermal maturation of the organic matter with which they are associated. We have conducted a series of artificial maturation experiments on two well-known immature organic-rich mudrocks, the Kimmeridge Blackstone Band (Late Jurassic age), and the Posidonia Shale (Early Jurassic age). These pyrolysis experiments allow us to trace changes in the composition of organic matter through varying stages of maturation, and the concentration and isotopic compositions of metals in rock residues and evolved organic fluids. Our results indicate that the thermal maturation of organic matter does not result in significant alteration of the isotopic compositions of Mo, Zn and Cd in the rock residues, which thus retain primary palaeodepositional information. Systematic increases in the concentrations of Mo, Zn and Cd in rock residues with progressively higher thermal maturity are attributed to the loss of substrate mass in the form of fluids released during pyrolysis-induced cracking of kerogen, and to the relatively low concentrations of Mo, Zn and Cd in these fluids. The Mo-isotope compositions of fluids produced during pyrolysis are isotopically similar to the bulk rock; in contrast the isotopic composition of Zn in organic fluids is ∼0.4–0.6‰ lighter than the bulk rock. The progressive loss of organic matter from rock residues during maturation coupled with the increases in metal concentrations leads to an increase of metal/TOC ratios, which may be up to double their original (syn-depositional) value in thermally mature rocks. This observation must be taken into account when using metal/TOC ratios as proxies for oceanic metal inventories throughout geological time. Finally, calculations using the mass of asphaltenes recovered during the pyrolysis experiments suggest that organically bound Mo, Zn and Cd account for several percent of the total rock metal inventory

Controls on the cadmium isotope composition of modern marine sediments

Continental margin sediments have been identified as the dominant sink in the marine budget of cadmium (Cd). The isotopic composition of this important output flux is, however, unknown. Here we present, with measurements on the Argentine continental margin, the first observational constraints on the isotopic composition of Cd in modern marine oxic and sub-oxic sediments. We identify two main removal mechanisms of Cd; in organic material, and by sulfide formation. Surface margin sediments (0–0.5 cm), with dissolved O2 below detection from ∼0.5 cm, are isotopically lighter than overlying oxygenated waters. A mass balance for these surface sediments indicates that Cd is present dominantly as organically-bound particulate Cd. In sub-surface sediments, Cd concentrations increase in the zone of nitrate reduction, and attain similar isotopic compositions as the water that overlies the sediment (i.e. ∼0.35‰ in deep waters). These observations are consistent with a downward diffusive flux of seawater Cd and redox-driven quantitative removal of that Cd during sulfide precipitation. In combination, these two routes of Cd removal lead to burial of isotopically light organic Cd in margin sub-oxic sediments that enables the global isotopic Cd budget to be balanced

Isotopic evidence for changes in the zinc cycle during Oceanic Anoxic Event 2 (Late Cretaceous)

Widespread deposition of organic-rich shales during the Late Cretaceous Oceanic Anoxic Event 2 (OAE 2, ca. 94 Ma) occurred during a period of significant global paleo-environmental and geochemical change. It has been proposed that an increase in nutrient input to the ocean during OAE 2 was the key mechanism that generated and sustained high rates of organic-matter burial over time scales of 103–105 yr. Zinc is a bio-essential micronutrient and the proportion of Zn burial in oxic sediments relative to burial in organic-rich continental margin sediments is reflected in its seawater isotope composition. The first Zn-isotope records dating from the Cretaceous are presented here from three coeval carbonate successions: two from Europe (southern England and southern Italy) and one from southern Mexico. The new data show reproducible stratigraphic Zn-isotope patterns in spatially and lithologically diverse carbonate successions. Excursions to lower Zn-isotope values may be linked to the input of magmatic Zn, changes in the proportion of Zn burial into organic-rich sediments, and the liberation of previously buried Zn during an episode of widespread seafloor re-oxygenation during OAE 2 (the Plenus Cold Event)

Controls on the barium isotope compositions of marine sediments

The accumulation of barium (Ba) in marine sediments is considered to be a robust proxy for export production, although this application can be limited by uncertainty in BaSO4 preservation and sediment mass accumulation rates. The Ba isotope compositions of marine sediments could potentially record insights into past changes in the marine Ba cycle, which should be insensitive to these limitations, enabling more robust interpretation of sedimentary Ba as a proxy. To investigate the controls on the Ba isotope compositions of marine sediments and their potential for paleo-oceanographic applications, we present the first Ba isotope compositions results for sediments, as well as overlying seawater depth profiles collected in the South Atlantic. Variations in Ba isotope compositions of the sediments predominantly reflect changes in the relative contributions of detrital and authigenic Ba sources, with open-ocean sediments constraining the isotope composition of authigenic Ba to be 138/134 Ba ≈ +0.1 ‰. This value is consistent with the average isotope composition inferred for sinking particulate Ba using simple mass balance models of Ba in the overlying water column and is hypothesized to reflect the removal of Ba from the upper water column with an associated isotopic fractionation of Δ 138/134 Ba diss - part ≈ +0.4 to +0.5. Perturbations to upper ocean Ba cycling, due to changes in export production and the supply of Ba via upwelling, should therefore be recorded by the isotope compositions of sedimentary authigenic Ba. Such insights will help to improve the reliable application of Ba accumulation rates in marine sediments as a proxy for past changes in export production

AI is a viable alternative to high throughput screening: a 318-target study

: High throughput screening (HTS) is routinely used to identify bioactive small molecules. This requires physical compounds, which limits coverage of accessible chemical space. Computational approaches combined with vast on-demand chemical libraries can access far greater chemical space, provided that the predictive accuracy is sufficient to identify useful molecules. Through the largest and most diverse virtual HTS campaign reported to date, comprising 318 individual projects, we demonstrate that our AtomNet® convolutional neural network successfully finds novel hits across every major therapeutic area and protein class. We address historical limitations of computational screening by demonstrating success for target proteins without known binders, high-quality X-ray crystal structures, or manual cherry-picking of compounds. We show that the molecules selected by the AtomNet® model are novel drug-like scaffolds rather than minor modifications to known bioactive compounds. Our empirical results suggest that computational methods can substantially replace HTS as the first step of small-molecule drug discovery