Metal-rich organic matter and hot continental passive margin: drivers for Devonian copper-cobalt-germanium mineralization in dolomitized reef-bearing carbonate platform.

The abundance and types of reef-bearing carbonate platforms reflect the evolution of Devonian climate, with conspicuous microbial-algal reefs in the warm Early and Late Devonian and sponge-coral reefs in the cooler Middle Devonian. A dolomitized Wenlock-Lower Devonian microbial-algal reef-bearing carbonate platform hosts epigenetic copper-cobalt-germanium (Cu-Co-Ge) sulfide mineralization at Ruby Creek-Bornite in the Brooks Range, Alaska. Here, we present rhenium-osmium (Re-Os) radiometric ages and molybdenum and sulfur (δ98/95Mo = +2.04 to +5.48‰ and δ34S = -28.5 to -1.8‰) isotope variations for individual Cu-Co-Fe sulfide phases along the paragenetic sequence carrollite-bornite-pyrite. In the context of a hot, extensional passive margin, greenhouse conditions in the Early Devonian favored restriction of platform-top seawater circulation and episodic reflux of oxidized brines during growth of the carbonaceous carbonate platform. Molybdenum and sulfur isotope data signal the stepwise reduction of hot brines carrying Cu during latent reflux and geothermal circulation for at least ca. 15 million years from the Early Devonian until Cu-Co sulfide mineralization ca. 379-378 million years ago (Ma) in the Frasnian, Late Devonian (weighted mean of Re-Os model ages of carrollite at 379 ± 15 Ma [n = 4]; Re-Os isochron age of bornite at 378 ± 15 Ma [n = 6]). On the basis of petrographic relationships between sulfides and solid bitumen, and the Mo and S isotope data for sulfides, we imply that the endowment in critical metals (e.g., Co, Ge, Re) in the Ruby Creek-Bornite deposit is linked to the activity of primary producers that removed trace metals from the warm Early Devonian seawater and concentrated Co, Ge, and Re in algal-bacterial organic matter in carbonate sediments. Supplementary Information: The online version contains supplementary material available at 10.1007/s00126-022-01123-1.

Redox control on the tungsten isotope composition of seawater.

Free oxygen represents an essential basis for the evolution of complex life forms on a habitable Earth. The isotope composition of redox-sensitive trace elements such as tungsten (W) can possibly trace the earliest rise of oceanic oxygen in Earth's history. However, the impact of redox changes on the W isotope composition of seawater is still unknown. Here, we report highly variable W isotope compositions in the water column of a redox-stratified basin (δ186/184W between +0.347 and +0.810 ‰) that contrast with the homogenous W isotope composition of the open ocean (refined δ186/184W of +0.543 ± 0.046 ‰). Consistent with experimental studies, the preferential scavenging of isotopically light W by Mn-oxides increases the δ186/184W of surrounding seawater, whereas the redissolution of Mn-oxides causes decreasing seawater δ186/184W. Overall, the distinctly heavy stable W isotopic signature of open ocean seawater mirrors predominantly fully oxic conditions in modern oceans. We expect, however, that the redox evolution from anoxic to hypoxic and finally oxic marine conditions in early Earth's history would have continuously increased the seawater δ186/184W. Stable W isotope compositions of chemical sediments that potentially preserve changing seawater W isotope signatures might therefore reflect global changes in marine redox conditions.

LDL-mimetic lipid nanoparticles prepared by surface KAT ligation for in vivo MRI of atherosclerosis.

Low-density lipoprotein (LDL)-mimetic lipid nanoparticles (LNPs), decorated with MRI contrast agents and fluorescent dyes, were prepared by the covalent attachment of apolipoprotein-mimetic peptide (P), Gd(iii)-chelate (Gd), and sulforhodamine B (R) moieties on the LNP surface. The functionalized LNPs were prepared using the amide-forming potassium acyltrifluoroborate (KAT) ligation reaction. The KAT groups on the surface of LNPs were allowed to react with the corresponding hydroxylamine (HA) derivatives of P and Gd to provide bi-functionalized LNPs (PGd-LNP). The reaction proceeded with excellent yields, as observed by ICP-MS (for B and Gd amounts) and MALDI-TOF-MS data, and did not alter the morphology of the LNPs (mean diameter: ca. 50 nm), as shown by DLS and cryoTEM analyses. With the help of the efficient KAT ligation, a high payload of Gd(iii)-chelate on the PGd-LNP surface (ca. 2800 Gd atoms per LNP) was successfully achieved and provided a high r 1 relaxivity (r 1 = 22.0 s-1 mM-1 at 1.4 T/60 MHz and 25 °C; r 1 = 8.2 s-1 mM-1 at 9.4 T/400 MHz and 37 °C). This bi-functionalized PGd-LNP was administered to three atherosclerotic apoE -/- mice to reveal the clear enhancement of atherosclerotic plaques in the brachiocephalic artery (BA) by MRI, in good agreement with the high accumulation of Gd in the aortic arch as shown by ICP-MS. The parallel in vivo MRI and ex vivo studies of whole mouse cryo-imaging were performed using triply functionalized LNPs with P, Gd, and R (PGdR-LNP). The clear presence of atherosclerotic plaques in BA was observed by ex vivo bright field cryo-imaging, and they were also observed by high emission fluorescent imaging. These directly corresponded to the enhanced tissue in the in vivo MRI of the identical mouse.

Covalent Surface Modification of Lipid Nanoparticles by Rapid Potassium Acyltrifluoroborate Amide Ligation.

Because of the recent increasing demand for the synthetic biomimetic nanoparticles as in vivo carriers of drugs and imaging probes, it is very important to develop reliable, stable, and orthogonal methods for surface functionalization of the particles. To address these issues, in this study, a recently reported chemoselective amide-forming ligation reaction [potassium acyltrifluoroborate (KAT) ligation] was employed for the first time, as a mean to provide the surface functionalization of particles for creating covalent attachments of bioactive molecules. A KAT derivative of oleic acid (OA-KAT, 1) was added to a mixture of three lipid components (triolein, phosphatidyl choline, and cholesteryl oleate), which have been commonly used as substrates for lipid nanoparticles. After sonication and extrusion in a buffer, successfully obtained lipid nanoparticles containing OA-KAT (NP-KAT) resulted to be well-dispersed with mean diameters of about 40-70 nm by dynamic light scattering. After preliminary confirmation of the fast and efficient KAT ligation in a solution phase using the identical reaction substrates, the "on-surface (on-particle)" KAT ligation on the NP-KAT was tested with an N-hydroxylamine derivative of fluorescein 2. The ligation was carried out in a phosphate buffer (10 mM, pH 5.2) at room temperature with reactant concentration ranges of 250 µM. Reaction efficiency was evaluated based on the amount of boron (determined by inductively coupled plasma mass spectrometry) and fluorescein (determined by fluorescence emission) in the particles before and after the reaction. As a result, the reaction proceeded in a significantly efficient way with ca. 40-50% conversion of the OA-KAT incorporated in the particles. Taken together with the fact that KAT ligation does not require any additional coupling reagents, these results indicated that the "on-surface" chemical functionalization of nanoparticles by KAT ligation is a useful method and represents a powerful and potentially versatile tool for the production of nanoparticles with a variety of covalently functionalized biomolecules and probes.

Zinc isotope fractionation during grain filling of wheat and a comparison of zinc and cadmium isotope ratios in identical soil-plant systems.

Remobilization of zinc (Zn) from shoot to grain contributes significantly to Zn grain concentrations and thereby to food quality. On the other hand, strong accumulation of cadmium (Cd) in grain is detrimental for food quality. Zinc concentrations and isotope ratios were measured in wheat shoots (Triticum aestivum) at different growth stages to elucidate Zn pathways and processes in the shoot during grain filling. Zinc mass significantly decreased while heavy Zn isotopes accumulated in straw during grain filling (Δ66 Znfull maturity-flowering  = 0.21-0.31‰). Three quarters of the Zn mass in the shoot moved to the grains, which were enriched in light Zn isotopes relative to the straw (Δ66 Zngrain-straw -0.21 to -0.31‰). Light Zn isotopes accumulated in phloem sinks while heavy isotopes were retained in phloem sources likely because of apoplastic retention and compartmentalization. Unlike for Zn, an accumulation of heavy Cd isotopes in grains has previously been shown. The opposing isotope fractionation of Zn and Cd might be caused by distinct affinities of Zn and Cd to oxygen, nitrogen, and sulfur ligands. Thus, combined Zn and Cd isotope analysis provides a novel tool to study biochemical processes that separate these elements in plants.

The oceanic budgets of nickel and zinc isotopes: the importance of sulfidic environments as illustrated by the Black Sea.

Isotopic data collected to date as part of the GEOTRACES and other programmes show that the oceanic dissolved pool is isotopically heavy relative to the inputs for zinc (Zn) and nickel (Ni). All Zn sinks measured until recently, and the only output yet measured for Ni, are isotopically heavier than the dissolved pool. This would require either a non-steady-state ocean or other unidentified sinks. Recently, isotopically light Zn has been measured in organic carbon-rich sediments from productive upwelling margins, providing a potential resolution of this issue, at least for Zn. However, the origin of the isotopically light sedimentary Zn signal is uncertain. Cellular uptake of isotopically light Zn followed by transfer to sediment does not appear to be a quantitatively important process. Here, we present Zn and Ni isotope data for the water column and sediments of the Black Sea. These data demonstrate that isotopically light Zn and Ni are extracted from the water column, probably through an equilibrium fractionation between different dissolved species followed by sequestration of light Zn and Ni in sulfide species to particulates and the sediment. We suggest that a similar, non-quantitative, process, operating in porewaters, explains the Zn data from organic carbon-rich sediments.This article is part of the themed issue 'Biological and climatic impacts of ocean trace element chemistry'.

Rise to modern levels of ocean oxygenation coincided with the Cambrian radiation of animals.

The early diversification of animals (∼ 630 Ma), and their development into both motile and macroscopic forms (∼ 575-565 Ma), has been linked to stepwise increases in the oxygenation of Earth's surface environment. However, establishing such a linkage between oxygen and evolution for the later Cambrian 'explosion' (540-520 Ma) of new, energy-sapping body plans and behaviours has proved more elusive. Here we present new molybdenum isotope data, which demonstrate that the areal extent of oxygenated bottom waters increased in step with the early Cambrian bioradiation of animals and eukaryotic phytoplankton. Modern-like oxygen levels characterized the ocean at ∼ 521 Ma for the first time in Earth history. This marks the first establishment of a key environmental factor in modern-like ecosystems, where animals benefit from, and also contribute to, the 'homeostasis' of marine redox conditions.

A biomarker based on the stable isotopes of nickel.

The new stable isotope systems of transition metals are increasingly used to understand and quantify the impact of primitive microbial metabolisms on the modern and ancient Earth. To date, little effort has been expended on nickel (Ni) isotopes but there are good reasons to believe that this system may be more straightforward, and useful in this respect, than some others. Here, we present Ni stable isotope data for abiotic terrestrial samples and pure cultures of methanogens. The dataset for rocks reveals little isotopic variability and provides a lithologic baseline for terrestrial Ni isotope studies. In contrast, methanogens assimilate the light isotopes, yielding residual media with a complementary heavy isotopic enrichment. Methanogenesis may have evolved during or before the Archean, when methane could have been key to Earth's early systems. Our data suggest significant potential in Ni stable isotopes for identifying and quantifying methanogenesis on the early planet. Additionally, Ni stable isotope fractionation may well prove to be the fundamental unambiguous trace metal biomarker for methanogens.