Xiangli Wang

Low Mid-Proterozoic atmospheric oxygen levels and the delayed rise of animals

Low oxygen limited the rise of animals Oxygen levels in Earths early atmosphere had an important influence on the evolution of complex life. Planavsky et al. analyzed the isotopic signature of chromium in sedimentary rocks from across the globe—a proxy for past oxygen levels. Oxygen levels in the mid-Proterozoic (1.6 billion to 900 million years ago) were very low: less than 0.1% of the modern atmosphere. These low levels were probably below the minimum oxygen requirements for the earliest animals, delaying their emergence and diversification. Science, this issue p. 635 Oxygen levels in Earth’s early atmosphere were often less than 1% of modern levels. The oxygenation of Earth’s surface fundamentally altered global biogeochemical cycles and ultimately paved the way for the rise of metazoans at the end of the Proterozoic. However, current estimates for atmospheric oxygen (O2) levels during the billion years leading up to this time vary widely. On the basis of chromium (Cr) isotope data from a suite of Proterozoic sediments from China, Australia, and North America, interpreted in the context of data from similar depositional environments from Phanerozoic time, we find evidence for inhibited oxidation of Cr at Earth’s surface in the mid-Proterozoic (1.8 to 0.8 billion years ago). These data suggest that atmospheric O2 levels were at most 0.1% of present atmospheric levels. Direct evidence for such low O2 concentrations in the Proterozoic helps explain the late emergence and diversification of metazoans.

A shale-hosted Cr isotope record of low atmospheric oxygen during the Proterozoic

The emergence and expansion of animal life on Earth represents a dramatic shift in the structure and complexity of the biosphere. A lack of firm constraints on surface oxygen levels during the mid-Proterozoic has resulted in heated debate as to whether the rise and earliest diversification of animals was directly linked to a change in environmental oxygen levels or, instead, simply reflects the timing of innovations in gene expression and developmental regulation and was independent of a direct environmental trigger. Here, we present chromium (Cr) isotope data from marine black shales that provide evidence for minimal Cr oxidation throughout the mid-Proterozoic leading up to the diversification of eukaryotes and the rise of animals during the late Neoproterozoic. This observation requires very low background oxygen levels (<1% of present atmospheric levels). Accepting previously proposed estimates of p O2 levels needed to induce Cr isotope fractionation, our data provide support for the persistence of an Earth system in which baseline atmospheric p O2 would have been low enough to inhibit the diversification of animals until ca. 800 Ma. More generally, evidence for a delayed rise of atmospheric oxygen strongly suggests that environmental factors have played a fundamental role in controlling the emergence and expansion of complex life on Earth.

Mobilization of arsenic in aquifers from the Datong Basin, China: Evidence from geochemical and iron isotopic data

Iron isotope compositions of various Fe pools in aquifer sediments were measured at a known As-contaminated site in the Datong Basin, China. The δ(56)Fe values of HCl-extracted poor-crystalline Fe(III) range widely from -0.41‰ to 0.36‰. We interpret the low Fe(II)/Fe(Extractable) ratios (<50%) and the negative correlation between Fe(II)/Fe(Extractable) and δ(56)Fe values in HCl-extracted poor-crystalline Fe to be best explained by redox cycling of Fe induced by microbial Fe(III) reduction. However, the high Fe(II)/Fe(Extractable) ratios (~/>70%) and positive correlation between Fe(II)/Fe(Extractable) and δ(56)Fe values for HCl-extracted poor-crystalline Fe indicates production of sulfides (FeSs). The δ(56)Fe values of crystalline Fe(III) extracted by reductant appears to be comparatively small varying from -0.01‰ to 0.24‰, which is consistent with the δ(56)Fe values for ferric oxides/hydroxides having undergone microbial Fe(III) reduction. The Fe isotope composition of various Fe pools shows the transformation between crystalline Fe(III) and poor-crystalline crystalline Fe(III) and the secondary Fe(II) phases has already occurred or is occurring in aquifer sediments. More importantly, there is a significant difference in the As concentrations in crystalline Fe(III) oxides/hydroxides and HCl-extracted Fe phases. The concentrations of As range from 1.6 to 29.9 mg kg(-1) and from 0.6 to 3.0 mg kg(-1), for crystalline Fe(III) and HCl-extracted Fe phases respectively. Accordingly, the transformation of Fe minerals induced by microbial Fe(III) reduction can contribute to the mobilization of As. This study is the first to examine the Fe isotope compositions in high As aquifer sediments; the results show that the Fe isotope would be an important tool in demonstrating the enrichment of As in groundwater.

A cenozoic seawater redox record derived from 238U/235U in ferromanganese crusts

Oceanic oxygen levels are projected to drop in certain areas due to warming climate, but the net effect to the overall ocean redox state is difficult to predict. Here we measured the “stable” uranium isotope composition (238U/235U) in globally representative hydrogenous ferromanganese crusts in order to reconstruct the redox evolution of the global ocean throughout the Cenozoic. Samples averaging ∼3 Myr intervals have analytically indistinguishable 238U/235U throughout the Cenozoic. Combined with a U isotope mass balance model, we suggest that the overall ocean redox state has remained remarkably stable on million year time scales throughout the Cenozoic, despite large surface temperature fluctuations during this time. This suggests that stabilizing feedbacks (for example, nutrient limitation in low oxygen zones) may have prevented dramatic large-scale shifts in oxygen levels in the ocean. However, the Fe-Mn crust record will be unlikely to reflect rapid perturbations in ocean redox state. To investigate these events, sediment archives with faster accumulation rates and redox proxies with faster response time must be explored.

Integrated geochemical-petrographic insights from component-selective δ238U of Cryogenian marine carbonates

Emerging geochemical proxies have improved our understanding of the broad-scale history of Earth’s oxygenation. However, paleoredox work does not always include extensive consideration of sample preservation and paleoenvironmental setting. This is particularly an issue with marine carbonates, which although being potentially ideal ocean redox archives, are commonly altered during diagenesis. Here we provide new insight into the robustness of uranium isotopes (238U/235U ratios: δ238U values) as paleoredox tracers by determining texture-specific δ238U values from a well-described Cryogenian (Balcanoona) reef complex in South Australia. We found high variability in δ238U values between different carbonate components, even within a single sample. Petrographically, the best-preserved components from the Balcanoona reef are marine cements, which have a mean δ238U value of −0.23‰, essentially unfractionated from riverine inputs. These values are interpreted as reflecting a marine system with widespread anoxic and iron-rich settings. Less-well-preserved phases have δ238U values spanning almost the entire extent of the documented isotopic range. This integrated petrographic-geochemical work demonstrates the need for petrographic analysis and careful sample selection on a case-by-case basis in future carbonate metal isotope geochemistry.

Chromium isotopic composition of core-top planktonic foraminifera

The chromium isotope system (53 Cr/52 Cr expressed as δ53 Cr relative to NIST SRM 979) is potentially a powerful proxy for the redox state of the ocean-atmosphere system, but a lack of temporally continuous, well-calibrated archives has limited its application to date. Marine carbonates could potentially serve as a common and continuous Cr isotope archive. Here, we present the first evaluation of planktonic foraminiferal calcite as an archive of seawater δ53 Cr. We show that single foraminiferal species from globally distributed core tops yielded variable δ53 Cr, ranging from 0.1‰ to 2.5‰. These values do not match with the existing measurements of seawater δ53 Cr. Further, within a single core-top, species with similar water column distributions (i.e., depth habitats) yielded variable δ53 Cr values. In addition, mixed layer and thermocline species do not consistently exhibit decreasing trends in δ53 Cr as expected based on current understanding of Cr cycling in the ocean. These observations suggest that either seawater δ53 Cr is more heterogeneous than previously thought or that there is significant and species-dependent Cr isotope fractionation during foraminiferal calcification. Given that the δ53 Cr variability is comparable to that observed in geological samples throughout Earths history, interpreting planktonic foraminiferal δ53 Cr without calibrating modern foraminifera further, and without additional seawater measurements, would lead to erroneous conclusions. Our core-top survey clearly indicates that planktonic foraminifera are not a straightforward δ53 Cr archive and should not be used to study marine redox evolution without additional study. It likewise cautions against the use of δ53 Cr in bulk carbonate or other biogenic archives pending further work on vital effects and the geographic heterogeneity of the Cr isotope composition of seawater.

Redox-independent chromium isotope fractionation induced by ligand-promoted dissolution

The chromium (Cr) isotope system has emerged as a potential proxy for tracing the Earth’s atmospheric evolution based on a redox-dependent framework for Cr mobilization and isotope fractionation. Although studies have demonstrated that redox-independent pathways can also mobilize Cr, no quantitative constraints exist on the associated isotope fractionations. Here we survey the effects of common environmental ligands on the dissolution of Cr(III)-(oxy)hydroxide solids and associated Cr isotope fractionation. For a variety of organic acids and siderophores, δ53Cr values of dissolved Cr(III) are −0.27 to 1.23‰, within the range of previously observed Cr isotope signatures in rock records linked to Cr redox cycling. Thus, ligand-promoted dissolution of Cr-containing solids, a redox-independent process, must be taken into account when using sedimentary Cr isotope signatures to diagnose atmospheric oxygen levels. This work provides a step towards establishing a more robust framework for using Cr isotopes to track the evolution of the Earth’s atmosphere.The chromium (Cr) isotope system has emerged as a potential proxy for tracing Earth’s atmospheric evolution based on a redox-dependent framework. Here the authors show that ligand-complexation, a redox-independent process, must be considered when using Cr isotope signatures to diagnose atmospheric oxygen levels.

The Molybdenum Isotope System as a Tracer of Slab Input in Subduction Zones: An Example From Martinique, Lesser Antilles Arc

Molybdenum isotopes are fractionated by Earth-surface processes and may provide a tracer for the recycling of crustal material into the mantle. Here, we examined the Mo isotope composition of arc lavas from Martinique in the Lesser Antilles arc, along with Cretaceous and Cenozoic Deep Sea Drilling Project sediments representing potential sedimentary inputs into the subduction zone. Mo stable isotope composition (defined as δ98Mo in ‰ deviation from the NIST 3134 standard) in lavas older than ∼7 million years (Ma) exhibits a narrow range similar to and slightly higher than MORB, whereas those younger than ∼7 Ma show a much greater range and extend to unusually low δ98Mo values. Sediments from DSDP Leg 78A, Site 543 have uniformly low δ98Mo values whereas Leg 14, Site 144 contains both sediments with isotopically light Mo and Mo-enriched black shales with isotopically heavy Mo. When coupled with published radiogenic isotope data, Mo isotope systematics of the lavas can be explained through binary mixing between a MORB-like end-member and different sedimentary compositions identified in the DSDP cores. The lavas older than ∼7 Ma were influenced by incorporation of isotopically heavy black shales into the mantle wedge. The younger lavas are the product of mixing isotopically light sedimentary material into the mantle wedge. The change in Mo isotope composition of the lavas at ∼7 Ma is interpreted to reflect the removal of the Cretaceous black shale component due to the arrival of younger ocean crust where the age-equivalent Cretaceous sediments were deposited in shallower oxic waters. Isotopic fractionation of Mo during its removal from the slab is not required to explain the observed systematics in this system.