Long-term sedimentary recycling of rare sulphur isotope anomalies

The accumulation of substantial quantities of O_2 in the atmosphere has come to control the chemistry and ecological structure of Earth’s surface. Non-mass-dependent (NMD) sulphur isotope anomalies in the rock record are the central tool used to reconstruct the redox history of the early atmosphere. The generation and initial delivery of these anomalies to marine sediments requires low partial pressures of atmospheric O_2 (PO_2; refs 2, 3), and the disappearance of NMD anomalies from the rock record 2.32 billion years ago is thought to have signalled a departure from persistently low atmospheric oxygen levels (less than about 10^(−5) times the present atmospheric level) during approximately the first two billion years of Earth’s history. Here we present a model study designed to describe the long-term surface recycling of crustal NMD anomalies, and show that the record of this geochemical signal is likely to display a ‘crustal memory effect’ following increases in atmospheric PO_2 above this threshold. Once NMD anomalies have been buried in the upper crust they are extremely resistant to removal, and can be erased only through successive cycles of weathering, dilution and burial on an oxygenated Earth surface. This recycling results in the residual incorporation of NMD anomalies into the sedimentary record long after synchronous atmospheric generation of the isotopic signal has ceased, with dynamic and measurable signals probably surviving for as long as 10–100 million years subsequent to an increase in atmospheric PO_2 to more than 10^(−5) times the present atmospheric level. Our results can reconcile geochemical evidence for oxygen production and transient accumulation with the maintenance of NMD anomalies on the early Earth, and suggest that future work should investigate the notion that temporally continuous generation of new NMD sulphur isotope anomalies in the atmosphere was likely to have ceased long before their ultimate disappearance from the rock record

Persistent global marine euxinia in the early Silurian

The second pulse of the Late Ordovician mass extinction occurred around the Hirnantian-Rhuddanian boundary (~444 Ma) and has been correlated with expanded marine anoxia lasting into the earliest Silurian. Characterization of the Hirnantian ocean anoxic event has focused on the onset of anoxia, with global reconstructions based on carbonate δ238U modeling. However, there have been limited attempts to quantify uncertainty in metal isotope mass balance approaches. Here, we probabilistically evaluate coupled metal isotopes and sedimentary archives to increase constraint. We present iron speciation, metal concentration, δ98Mo and δ238U measurements of Rhuddanian black shales from the Murzuq Basin, Libya. We evaluate these data (and published carbonate δ238U data) with a coupled stochastic mass balance model. Combined statistical analysis of metal isotopes and sedimentary sinks provides uncertainty-bounded constraints on the intensity of Hirnantian-Rhuddanian euxinia. This work extends the duration of anoxia to >3 Myrs – notably longer than well-studied Mesozoic ocean anoxic events

Chromium isotope fractionation during subduction-related metamorphism, black shale weathering, and hydrothermal alteration

© The Author(s), 2016. This is the author's version of the work and is distributed under the terms of the Creative Commons Attribution License. The definitive version was published in Chemical Geology 423 (2016): 19-33, doi:10.1016/j.chemgeo.2016.01.003.Chromium (Cr) isotopes are an emerging proxy for redox processes at Earth’s surface. However, many geological reservoirs and isotope fractionation processes are still not well understood. The purpose of this contribution is to move forward our understanding of (1) Earth’s high temperature Cr isotope inventory and (2) Cr isotope fractionations during subduction-related metamorphism, black shale weathering and hydrothermal alteration. The examined basalts and their metamorphosed equivalents yielded δ53Cr values falling within a narrow range of -0.12±0.13‰ (2SD, n=30), consistent with the previously reported range for the bulk silicate Earth (BSE). Compilations of currently available data for fresh silicate rocks (43 samples), metamorphosed silicate rocks (50 samples), and mantle chromites (39 samples) give δ53Cr values of -0.13±0.13‰, -0.11±0.13‰, and -0.07±0.13‰, respectively. Although the number of high-temperature samples analyzed has tripled, the originally proposed BSE range appears robust. This suggests very limited Cr isotope fractionation under high temperature conditions. Additionally, in a highly altered metacarbonate transect that is representative of fluid-rich regional metamorphism, we did not find resolvable variations in δ53Cr, despite significant loss of Cr. This work suggests that primary Cr isotope signatures may be preserved even in instances of intense metamorphic alteration at relatively high fluid-rock ratios. Oxidative weathering of black shale at low pH creates isotopically heavy mobile Cr(VI). However, a significant proportion of the Cr(VI) is apparently immobilized near the weathering surface, leading to local enrichment of isotopically heavy Cr (δ53Cr values up to ~0.5‰). The observed large Cr isotope variation in the black shale weathering profile provides indirect evidence for active manganese oxide formation, which is primarily controlled by microbial activity. Lastly, we found widely variable δ53Cr (-0.2‰ to 0.6‰) values in highly serpentinized peridotites from ocean drilling program drill cores and outcropping ophiolite sequences. The isotopically heavy serpentinites are most easily explained through a multi-stage alteration processes: Cr loss from the host rock under oxidizing conditions, followed by Cr enrichment under sulfate reducing conditions. In contrast, Cr isotope variability is limited in mildly altered mafic oceanic crust.Funding for this research was provided by Agouron Institute to XLW, National Science Foundation (NSF) EAR-0105927 and EAR-1250269 to JJA, and NSF EAR-1324566 to ES. NJP and CTR acknowledge funding from the Alternative Earths NAI.2017-01-1

No evidence for high atmospheric oxygen levels 1,400 million years ago

Zhang et al. (1) recently proposed atmospheric oxygen levels of ∼4% present atmospheric levels (PAL) based on modeling a paleoenvironment reconstructed from trace metal and biomarker data from the 1,400 Ma Xiamaling Formation in China. Intriguingly, this pO2 level is above the threshold oxygen requirements of basal animals and clashes with evidence for atmospheric oxygen levels <<1% PAL in the mid-Proterozoic (2). However, there are fundamental problems with the inorganic and organic geochemical work presented by Zhang et al. (1)

Proterozoic ocean redox and biogeochemical stasis

The partial pressure of oxygen in Earth’s atmosphere has increased dramatically through time, and this increase is thought to have occurred in two rapid steps at both ends of the Proterozoic Eon (∼2.5–0.543 Ga). However, the trajectory and mechanisms of Earth’s oxygenation are still poorly constrained, and little is known regarding attendant changes in ocean ventilation and seafloor redox. We have a particularly poor understanding of ocean chemistry during the mid-Proterozoic (∼1.8–0.8 Ga). Given the coupling between redox-sensitive trace element cycles and planktonic productivity, various models for mid-Proterozoic ocean chemistry imply different effects on the biogeochemical cycling of major and trace nutrients, with potential ecological constraints on emerging eukaryotic life. Here, we exploit the differing redox behavior of molybdenum and chromium to provide constraints on seafloor redox evolution by coupling a large database of sedimentary metal enrichments to a mass balance model that includes spatially variant metal burial rates. We find that the metal enrichment record implies a Proterozoic deep ocean characterized by pervasive anoxia relative to the Phanerozoic (at least ∼30–40% of modern seafloor area) but a relatively small extent of euxinic (anoxic and sulfidic) seafloor (less than ∼1–10% of modern seafloor area). Our model suggests that the oceanic Mo reservoir is extremely sensitive to perturbations in the extent of sulfidic seafloor and that the record of Mo and chromium enrichments through time is consistent with the possibility of a Mo–N colimited marine biosphere during many periods of Earth’s history

Textural and geochemical features of freshwater microbialites from Laguna Bacalar, Quintana Roo, Mexico

Microbialites provide some of the oldest direct evidence of life on Earth. They reached their peak during the Proterozoic and declined afterward. Their decline has been attributed to grazing and/or burrowing by metazoans, to changes in ocean chemistry, or to competition with other calcifying organisms. The freshwater microbialites at Laguna Bacalar (Mexico) provide an opportunity to better understand microbialite growth in terms of interaction between grazing organisms versus calcium carbonate precipitation. The Laguna Bacalar microbialites are described in terms of their distinct mesostructures. Stromatolites display internal lamination, attributed to the precipitation of calcite and the upward migration of cyanobacteria during periods of low sedimentation. Thrombolitic stromatolites show internal lamination in addition to internal clotting. The clotting is seen as a result of binding and/or trapping of micritic peloids by cyanobacteria and attributed to periods of high sedimentation. The carbonates in both microbialites had similar C- and O-stable–isotopic signatures, both enriched in ^(13)C relative to bivalves, suggesting photosynthetic CO_2 uptake was the trigger for carbonate precipitation. This implies that the rate of microbialite growth is largely a function of ambient carbonate saturation state, while the texture is especially dependent on accretion rates and sediment deposition on their surface. Importantly, the coexistence with grazing animals suggests no significant inhibition on microbialite growth, thereby calling into question the decline of microbialite as a result of metazoan evolution. Varying sedimentation rates are likely important in controlling the distribution of thrombolite–stromatolite packages in the geological record, given the importance of this factor at Bacalar

Authigenic iron oxide proxies for marine zinc over geological time and implications for eukaryotic metallome evolution

Author Posting. © The Author(s), 2012. This is the author's version of the work. It is posted here by permission of John Wiley & Sons for personal use, not for redistribution. The definitive version was published in Geobiology 11 (2013): 295-306, doi:10.1111/gbi.12036.Here we explore enrichments in paleomarine Zn as recorded by authigenic iron oxides including Precambrian iron formations, ironstones and Phanerozoic hydrothermal exhalites. This compilation of new and literature-based iron formation analyses track dissolved Zn abundances and constrain the magnitude of the marine reservoir over geological time. Overall, the iron formation record is characterized by a fairly static range in Zn/Fe ratios throughout the Precambrian, consistent with the shale record (Scott et al., 2013, Nature Geoscience, 6, 125-128). When hypothetical partitioning scenarios are applied to this record, paleomarine Zn concentrations within about an order of magnitude of modern are indicated. We couple this examination with new chemical speciation models used to interpret the iron formation record. We present two scenarios: first, under all but the most sulfidic conditions and with Zn binding organic ligand concentrations similar to modern oceans, the amount of bioavailable Zn remained relatively unchanged through time. Late proliferation of Zn in eukaryotic metallomes has previously been linked to marine Zn biolimitation, but under this scenario, the expansion in eukaryotic Zn metallomes may be better linked to biologically intrinsic evolutionary factors. In this case zinc’s geochemical and biological evolution may be decoupled, and viewed as a function of increasing need for genome regulation and diversification of Zn-binding transcription factors. In the second scenario, we consider Archean organic ligand complexation in such excess that it may render Zn bioavailability low. However, this is dependent on Zn organic ligand complexes not being bioavailable, which remains unclear. In this case, although bioavailability may be low, sphalerite precipitation is prevented, thereby maintaining a constant Zn inventory throughout both ferruginous and euxinic conditions. These results provide new perspectives and constraints 50 on potential couplings between the trajectory of biological and marine geochemical coevolution.This work was supported by a NSERC Discovery Grant to KOK, a NSERC PDF to SVL, a NSERC CGSM to LJR, and an NSF-EAR-PDF to NJP. MAS acknowledges support from the Gordon and Betty Moore Foundation Grant #2724. This work was also supported by grants from the Deutsche Forschungsgemeinschaft (DFG) to A.K. (KA 1736/4-1 and 12-1)