Ernesto Pecoits

Oceanic nickel depletion and a methanogen famine before the Great Oxidation Event

It has been suggested that a decrease in atmospheric methane levels triggered the progressive rise of atmospheric oxygen, the so-called Great Oxidation Event, about 2.4 Gyr ago. Oxidative weathering of terrestrial sulphides, increased oceanic sulphate, and the ecological success of sulphate-reducing microorganisms over methanogens has been proposed as a possible cause for the methane collapse, but this explanation is difficult to reconcile with the rock record. Banded iron formations preserve a history of Precambrian oceanic elemental abundance and can provide insights into our understanding of early microbial life and its influence on the evolution of the Earth system. Here we report a decline in the molar nickel to iron ratio recorded in banded iron formations about 2.7 Gyr ago, which we attribute to a reduced flux of nickel to the oceans, a consequence of cooling upper-mantle temperatures and decreased eruption of nickel-rich ultramafic rocks at the time. We measured nickel partition coefficients between simulated Precambrian sea water and diverse iron hydroxides, and subsequently determined that dissolved nickel concentrations may have reached ∼400 nM throughout much of the Archaean eon, but dropped below ∼200 nM by 2.5 Gyr ago and to modern day values (∼9 nM) by ∼550 Myr ago. Nickel is a key metal cofactor in several enzymes of methanogens and we propose that its decline would have stifled their activity in the ancient oceans and disrupted the supply of biogenic methane. A decline in biogenic methane production therefore could have occurred before increasing environmental oxygenation and not necessarily be related to it. The enzymatic reliance of methanogens on a diminishing supply of volcanic nickel links mantle evolution to the redox state of the atmosphere.

Aerobic bacterial pyrite oxidation and acid rock drainage during the Great Oxidation Event

The enrichment of redox-sensitive trace metals in ancient marine sedimentary rocks has been used to determine the timing of the oxidation of the Earth’s land surface. Chromium (Cr) is among the emerging proxies for tracking the effects of atmospheric oxygenation on continental weathering; this is because its supply to the oceans is dominated by terrestrial processes that can be recorded in the Cr isotope composition of Precambrian iron formations. However, the factors controlling past and present seawater Cr isotope composition are poorly understood. Here we provide an independent and complementary record of marine Cr supply, in the form of Cr concentrations and authigenic enrichment in iron-rich sedimentary rocks. Our data suggest that Cr was largely immobile on land until around 2.48 Gyr ago, but within the 160 Myr that followed—and synchronous with independent evidence for oxygenation associated with the Great Oxidation Event (see, for example, refs 4–6)—marked excursions in Cr content and Cr/Ti ratios indicate that Cr was solubilized at a scale unrivalled in history. As Cr isotope fractionations at that time were muted, Cr must have been mobilized predominantly in reduced, Cr(iii), form. We demonstrate that only the oxidation of an abundant and previously stable crustal pyrite reservoir by aerobic-respiring, chemolithoautotrophic bacteria could have generated the degree of acidity required to solubilize Cr(iii) from ultramafic source rocks and residual soils. This profound shift in weathering regimes beginning at 2.48 Gyr ago constitutes the earliest known geochemical evidence for acidophilic aerobes and the resulting acid rock drainage, and accounts for independent evidence of an increased supply of dissolved sulphate and sulphide-hosted trace elements to the oceans around that time. Our model adds to amassing evidence that the Archaean-Palaeoproterozoic boundary was marked by a substantial shift in terrestrial geochemistry and biology.

Bilaterian burrows and grazing behavior at >585 million years ago

Early Burrowers Direct fossil evidence of animals from Ediacaran period—the time in Earths history just before extensive animal diversification in the Cambrian—is scant. However, the remains of animal activity in sediment, which remain intact through geologic time can provide clues about animal behavior and evolution. Pecoits et al. (p. 1693; see the Perspective by Droser and Gehling) found a suite of fossil animal burrows in sedimentary rocks in Uruguay. Radiometric dating places the age of the structures at ∼585 million years old, coinciding with the likely emergence of stem-group bilaterians. The complex morphologies of the fossil burrows suggest that these animals actively grazed and had the ability to burrow deep within sediments. Neoproterozoic trace fossils from Uruguay indicate that early animals appeared at a time between global glaciations. Based on molecular clocks and biomarker studies, it is possible that bilaterian life emerged early in the Ediacaran, but at present, no fossils or trace fossils from this time have been reported. Here we report the discovery of the oldest bilaterian burrows in shallow-water glaciomarine sediments from the Tacuarí Formation, Uruguay. Uranium-lead dating of zircons in cross-cutting granite dykes constrains the age of these burrows to be at least 585 million years old. Their features indicate infaunal grazing activity by early eumetazoans. Active backfill within the burrow, an ability to wander upward and downward to exploit shallowly situated sedimentary laminae, and sinuous meandering suggest advanced behavioral adaptations. These findings unite the paleontological and molecular data pertaining to the evolution of bilaterians, and link bilaterian origins to the environmental changes that took place during the Neoproterozoic glaciations.

Southernmost Exposures of the Arroyo del Soldado Group (Vendian to Cambrian, Uruguay): Palaeogeographic Implications for the Amalgamation of W-Gondwana

Abstract The occurrence of the Vendian to lowermost Cambrian Arroyo del Soldado Group (ASG) is reported from an area located to the SW of Minas, which was formerly mapped as part of the Lavalleja Group. The Yerbal, Polanco and Cerro Espuelitas Formations of the ASG occur there as a rather continuous, microfossil-rich sedimentary cover, intruded by granites of probable Cambrian age (Minas Granite). Organic-walled microfossils recovered from the Yerbal and Polanco Formations include Bavlinella faveolata, Leiosphaeridia tenuissima, Soldadophycus bossii, Soldadophycus major, Siphonophycus solidum, Glenobotrydion aenigmatis, and filament mats. The acritarch Dyctiotidium sp. is described for the first time from the Yerbal Formation. Essentially the same microfossil assemblage occurs in five samples of this unit collected immediately to the north of Minas. No identifiable microfossils were found in fifteen samples of organic-rich lithologies of the Lavalleja Group. Based on detailed geological mapping, litho- and biostratigraphic data, we show that the contact between the Arroyo del Soldado and Lavalleja Groups is of tectonic nature (Arroyo La Plata Lineament), the latter being pre-Vendian in age. The Villa Serrana Block is defined, and consists of the Carape and Lavalleja Groups, Las Ventanas and Playa Hermosa Formations, an unnamed siliciclastic-ultrabasic succession showing low-grade metamorphism, and various granitic intrusions mostly of Neoproterozoic to Cambrian age. Its boundaries are the Sarandi del Yi-Piriapolis shear zone to the W, the Sierra Ballena shear zone to the E, the Arroyo La Plata Lineament to the N, and the Rio de la Plata to the S. The Villa Serrana Block could be an allochthonous terrane, or alternatively, a part of the Nico Perez Terrane that was thrusted onto the ASG. No continuity exists between the Brusque and Porongos groups of southern Brazil and the Lavalleja Group. According to available data these units are probably not coeval, and do not represent the suture between the cratonic areas to the W (Rio de la Plata Craton) and the remnants of a Neoproterozoic magmatic arc to the E (Cuchilla Dionisio-Pelotas Terrane). Accretion of these blocks was controlled by sinistral, continental-scale megashears. The geology of the area is far too complex to be explained in terms of a single orogeny following one Wilson cycle.

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

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 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, zincs 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 on potential couplings between the trajectory of biological and marine geochemical coevolution.

Atmospheric hydrogen peroxide and Eoarchean iron formations

It is widely accepted that photosynthetic bacteria played a crucial role in Fe(II) oxidation and the precipitation of iron formations (IF) during the Late Archean-Early Paleoproterozoic (2.7-2.4 Ga). It is less clear whether microbes similarly caused the deposition of the oldest IF at ca. 3.8 Ga, which would imply photosynthesis having already evolved by that time. Abiological alternatives, such as the direct oxidation of dissolved Fe(II) by ultraviolet radiation may have occurred, but its importance has been discounted in environments where the injection of high concentrations of dissolved iron directly into the photic zone led to chemical precipitation reactions that overwhelmed photooxidation rates. However, an outstanding possibility remains with respect to photochemical reactions occurring in the atmosphere that might generate hydrogen peroxide (H2 O2 ), a recognized strong oxidant for ferrous iron. Here, we modeled the amount of H2 O2 that could be produced in an Eoarchean atmosphere using updated solar fluxes and plausible CO2 , O2 , and CH4 mixing ratios. Irrespective of the atmospheric simulations, the upper limit of H2 O2 rainout was calculated to be <10(6) molecules cm(-2) s(-1) . Using conservative Fe(III) sedimentation rates predicted for submarine hydrothermal settings in the Eoarchean, we demonstrate that the flux of H2 O2 was insufficient by several orders of magnitude to account for IF deposition (requiring ~10(11) H2 O2 molecules cm(-2) s(-1) ). This finding further constrains the plausible Fe(II) oxidation mechanisms in Eoarchean seawater, leaving, in our opinion, anoxygenic phototrophic Fe(II)-oxidizing micro-organisms the most likely mechanism responsible for Earths oldest IF.

The Archean Nickel Famine Revisited

Iron formations (IF) preserve a history of Precambrian oceanic elemental abundance that can be exploited to examine nutrient limitations on early biological productivity. However, in order for IF to be employed as paleomarine proxies, lumped-process distribution coefficients for the element of interest must be experimentally determined or assumed. This necessitates consideration of bulk ocean chemistry and which authigenic ferric iron minerals controlled the sorption reactions. It also requires an assessment of metal mobilization reactions that might have occurred in the water column during particle descent and during post-depositional burial. Here, we summarize recent developments pertaining to the interpretation and fidelity of the IF record in reconstructions of oceanic trace element evolution. Using an updated compilation, we reexamine and validate temporal trends previously reported for the nickel content in IF (see Konhauser et al., 2009 ). Finally, we reevaluate the consequences of methanogen Ni starvation in the context of evolving views of the Archean ocean-climate system and how the Ni famine may have ultimately facilitated the rise in atmospheric oxygen.

Response to Comment on "Bilaterian Burrows and Grazing Behavior at >585 Million Years Ago"

Gaucher et al. suggest that their field observations and petrographic analysis of one thin section do not support an Ediacaran age for the trace fossils–bearing strata of the Tacuarí Formation. We have strengthened our conclusion of an Ediacaran age for the Tacuarí Formation based on reassessment of new and previously presented field and petrographic evidence.

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

ABSTRACT 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 13C relative to bivalves, suggesting photosynthetic CO2 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.

Earliest evidence of bilaterians

Life has existed on Earth for almost 4 billion years, but most major groups of animals only appear i…