Chromium isotopes in marine hydrothermal sediments

Hydrothermal chromium (Cr) cycling contributes to marine Cr inventories and their Cr isotopic composition, yet Cr isotope effects associated with this cycling remain poorly documented. Here we determine the distribution, isotopic composition, and diagenetic mobility of Cr in hydrothermal sediments from the distal flank of the South East Pacific Rise (SEPR, DSDP-site 598). We find that Cr is primarily associated with the metalliferous iron (oxyhydr) oxide and detrital components of the sediment (0.4–3.6 mg kg⁻¹), whereas Cr concentrations are much lower in the dominant carbonate phase (80% Cr from the sediment relative to Fe. We propose this loss is tied to oxidation of authigenic Cr(III) to Cr(VI) followed by diagenetic remobilization and efflux from the sediment pile. The bulk δ⁵³Cr composition of the SEPR sediments is isotopically light (−0.24 to −0.57 ± 0.05‰) and the authigenic δ⁵³Cr is as light as −1.2 ± 0.2‰, and we argue that this light Cr isotopic composition results from the partial reduction of oxic seawater-bearing Cr(VI) by reduced hydrothermal vent fluids enriched in Fe(II)aq. Diagenetic oxidation of the reactive Cr pool by Mn-oxides and loss of Cr(VI) from the sediment may further deplete the sediment in ⁵³Cr during diagenesis. The δ⁵³Cr composition of the detrital Cr fraction of the sediment (average δ⁵³Cr composition = −0.05 ± 0.04‰) falls within the igneous silicate earth (ISE) range, revealing that detrital Cr delivered to this region of the Pacific ocean is unfractionated, and has carried a relatively constant δ⁵³Cr composition over the last 5.7 million years. Together our results show that light δ⁵³Cr compositions in hydrothermal sediments are imparted through a combination of processes previously overlooked in the marine Cr biogeochemical cycle, and that the δ⁵³Cr composition of such sediments may provide a rich source of information on paleo-marine redox conditions

Experimental study of Cu isotope fractionation during the reaction of aqueous Cu(II) with Fe(II) sulphides at temperatures between 40 and 200 degrees C

We present results of an experimental study on Cu isotope fractionation during the reaction of aqueous Cu(II) with Fe(II) sulphides: pyrrhotite and pyrite. The reaction was investigated under a range of experimental conditions, including time, temperature, initial Cu concentration in the solution, presence of a complexing ligand (acetate), and mineral to solution ratio. The reaction develops a series of mixed Cu–Fe and Cu sulphides. Cu isotope composition of reacted solutions and minerals determined by MCICP-MS attests to significant isotope fractionation that accompanies this reaction. The measured ∆65Cusolution − minerals values range from 1.97 to 3.23‰ δ65Cu, with an average of 2.64‰ δ65Cu. Observed shifts in Cu isotopic composition with reaction progress are explained by preferential transfer of the lighter Cu isotope, 63Cu, from solution into the mineral. It is proposed that Cu(II) to Cu(I) reduction step is the key control of the magnitude of observed isotope fractionation, while other factors, such as presence of complexing ligands, play minor role. This kinetic fractionation process is, however, affected by some degree of isotopic exchange and equilibration between Cu in the neoformed minerals and in the solution, at least in samples representing higher reaction extent. The results from 150 and 200 °C runs suggest that significant isotope fractionation occurs even at these elevated temperatures (∆65Cusolution − minerals above 2‰ δ65Cu). The results of this study suggest that that the reaction of aqueous Cu(II) with Fe(II) sulphides may be an important process in generating depleted δ65Cu signatures found in Cu-rich sulphides formed at low temperatures, such as seafloor hydrothermal vents or sediment-hosted stratified copper deposits

A lithium-isotope perspective on the evolution of carbon and silicon cycles

The evolution of the global carbon and silicon cycles is thought to have contributed to the long-term stability of Earth's climate. Many questions remain, however, regarding the feedback mechanisms at play, and there are limited quantitative constraints on the sources and sinks of these elements in Earth's surface environments. Here we argue that the lithium-isotope record can be used to track the processes controlling the long-term carbon and silicon cycles. By analysing more than 600 shallow-water marine carbonate samples from more than 100 stratigraphic units, we construct a new carbonate-based lithium-isotope record spanning the past 3 billion years. The data suggest an increase in the carbonate lithium-isotope values over time, which we propose was driven by long-term changes in the lithium-isotopic conditions of sea water, rather than by changes in the sedimentary alterations of older samples. Using a mass-balance modelling approach, we propose that the observed trend in lithium-isotope values reflects a transition from Precambrian carbon and silicon cycles to those characteristic of the modern. We speculate that this transition was linked to a gradual shift to a biologically controlled marine silicon cycle and the evolutionary radiation of land plants

SIRT6 Promotes Hepatic Beta-Oxidation via Activation of PPARα

The pro-longevity enzyme SIRT6 regulates various metabolic pathways. Gene expression analyses in SIRT6 heterozygotic mice identify significant decreases in PPARα signaling, known to regulate multiple metabolic pathways. SIRT6 binds PPARα and its response element within promoter regions and activates gene transcription. Sirt6+/− results in significantly reduced PPARα-induced β-oxidation and its metabolites and reduced alanine and lactate levels, while inducing pyruvate oxidation. Reciprocally, starved SIRT6 transgenic mice show increased pyruvate, acetylcarnitine, and glycerol levels and significantly induce β-oxidation genes in a PPARα-dependent manner. Furthermore, SIRT6 mediates PPARα inhibition of SREBP-dependent cholesterol and triglyceride synthesis. Mechanistically, SIRT6 binds PPARα coactivator NCOA2 and decreases liver NCOA2 K780 acetylation, which stimulates its activation of PPARα in a SIRT6-dependent manner. These coordinated SIRT6 activities lead to regulation of whole-body respiratory exchange ratio and liver fat content, revealing the interactions whereby SIRT6 synchronizes various metabolic pathways, and suggest a mechanism by which SIRT6 maintains healthy liver

Evidence for oxygenic photosynthesis half a billion years before the Great Oxidation Event

The early Earth was characterized by the absence of oxygen in the ocean–atmosphere system, in contrast to the well-oxygenated conditions that prevail today. Atmospheric concentrations first rose to appreciable levels during the Great Oxidation Event, roughly 2.5–2.3 Gyr ago. The evolution of oxygenic photosynthesis is generally accepted to have been the ultimate cause of this rise, but it has proved difficult to constrain the timing of this evolutionary innovation. The oxidation of manganese in the water column requires substantial free oxygen concentrations, and thus any indication that Mn oxides were present in ancient environments would imply that oxygenic photosynthesis was ongoing. Mn oxides are not commonly preserved in ancient rocks, but there is a large fractionation of molybdenum isotopes associated with the sorption of Mo onto the Mn oxides that would be retained. Here we report Mo isotopes from rocks of the Sinqeni Formation, Pongola Supergroup, South Africa. These rocks formed no less than 2.95 Gyr ago in a nearshore setting. The Mo isotopic signature is consistent with interaction with Mn oxides. We therefore infer that oxygen produced through oxygenic photosynthesis began to accumulate in shallow marine settings at least half a billion years before the accumulation of significant levels of atmospheric oxygen

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

Copper and tin isotopic analysis of ancient bronzes for archaeological investigation: development and validation of a suitable analytical methodology

Although in many cases Pb isotopic analysis can be relied on for provenance determination of ancient bronzes, sometimes the use of “non-traditional” isotopic systems, such as those of Cu and Sn, is required. The work reported on in this paper aimed at revising the methodology for Cu and Sn isotope ratio measurements in archaeological bronzes via optimization of the analytical procedures in terms of sample pre-treatment, measurement protocol, precision, and analytical uncertainty. For Cu isotopic analysis, both Zn and Ni were investigated for their merit as internal standard (IS) relied on for mass bias correction. The use of Ni as IS seems to be the most robust approach as Ni is less prone to contamination, has a lower abundance in bronzes and an ionization potential similar to that of Cu, and provides slightly better reproducibility values when applied to NIST SRM 976 Cu isotopic reference material. The possibility of carrying out direct isotopic analysis without prior Cu isolation (with AG-MP-1 anion exchange resin) was investigated by analysis of CRM IARM 91D bronze reference material, synthetic solutions, and archaeological bronzes. Both procedures (Cu isolation/no Cu isolation) provide similar δ 65Cu results with similar uncertainty budgets in all cases (±0.02–0.04 per mil in delta units, k = 2, n = 4). Direct isotopic analysis of Cu therefore seems feasible, without evidence of spectral interference or matrix-induced effect on the extent of mass bias. For Sn, a separation protocol relying on TRU-Spec anion exchange resin was optimized, providing a recovery close to 100 % without on-column fractionation. Cu was recovered quantitatively together with the bronze matrix with this isolation protocol. Isotopic analysis of this Cu fraction provides δ 65Cu results similar to those obtained upon isolation using AG-MP-1 resin. This means that Cu and Sn isotopic analysis of bronze alloys can therefore be carried out after a single chromatographic separation using TRU-Spec resin. Tin isotopic analysis was performed relying on Sb as an internal standard used for mass bias correction. The reproducibility over a period of 1 month (n = 42) for the mass bias-corrected Sn isotope ratios is in the range of 0.06–0.16 per mil (2 s), for all the ratios monitored

PLANET TOPERS: Planets, Tracing the Transfer, Origin, Preservation, and Evolution of their ReservoirS

The Interuniversity Attraction Pole (IAP) ‘PLANET TOPERS’ (Planets: Tracing the Transfer, Origin, Preservation, and Evolution of their Reservoirs) addresses the fundamental understanding of the thermal and compositional evolution of the different reservoirs of planetary bodies (core, mantle, crust, atmosphere, hydrosphere, cryosphere, and space) considering interactions and feedback mechanisms. Here we present the first results after 2 years of project work. © 2016, Springer Science+Business Media Dordrecht

Molybdenum record from black shales indicates oscillating atmospheric oxygen levels in the early Paleoproterozoic

The early Paleoproterozoic witnessed Earth's first major oxygenation, referred to as the Great Oxidation Event or GOE. The GOE began around 2.45 billion years ago (Ga) and progressed over hundreds of millions of years, as evidenced by multiple redox indicators, before coming to an abrupt end by ca. 2.06 Ga. The details of the GOE and the extent of oxygenation are still not resolved, however, and it is not clear how redox conditions across the GOE compare with those during the middle Proterozoic. In order to investigate the evolution of deep-ocean redox conditions during the GOE, we present Mo concentration and isotope data together with Fe speciation values for three key organic matter-rich shale units of the early Paleoproterozoic age (2.32–2.06 Ga). In addition, we present a new graphical representation of modeling suggesting that the oceanic Mo isotope system is highly sensitive to the balance between anoxic/suboxic and euxinic conditions until deep-ocean oxygenation, similar in scale to modern ocean oxygenation, is reached. Our approach indicates rising, yet oscillating atmospheric oxygen at 2.32 Ga, leading to an abrupt increase in Mo supply to the oceans and large Mo isotope variations under non-steady state conditions. The low seawater δ98Mo value based on the ca. 2.32 Ga black shales (0.32 ± 0.58‰) suggests that the oceans were still largely anoxic with locally developed euxinic conditions. Between 2.2 and 2.1 Ga, during the peak of the Lomagundi carbon isotope excursion, we observe higher δ98MoSW values (1.23 ± 0.36‰) together with lower Mo concentrations in euxinic shales ([Mo] = 6.3 ± 9.0 ppm). We suggest that a decrease in the continental Mo input flux in the later part of the GOE was the main cause of this trend. Lower sulfide availability on the continents after protracted sulfide weathering associated with the early stages of the GOE, and efficient Mo removal in poorly oxygenated oceans under weakly euxinic conditions would both have contributed to the contraction of the Mo oceanic reservoir. By ca. 2.06 Ga, the Mo isotope composition of seawater, as inferred from euxinic black shale intervals, became significantly lighter (0.70 ± 0.21‰), reflecting an increased rate of quantitative Mo removal due to the more widespread development of strongly euxinic conditions. Counterintuitively, seawater Mo concentrations recovered, likely due to an increase in the Mo input, which in turn might reflect enhanced weathering of organic carbon-rich shales deposited during the Lomagundi Event