Leslie J. Robbins

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.

Evolution of the global phosphorus cycle

The macronutrient phosphorus is thought to limit primary productivity in the oceans on geological timescales. Although there has been a sustained effort to reconstruct the dynamics of the phosphorus cycle over the past 3.5 billion years, it remains uncertain whether phosphorus limitation persisted throughout Earth’s history and therefore whether the phosphorus cycle has consistently modulated biospheric productivity and ocean–atmosphere oxygen levels over time. Here we present a compilation of phosphorus abundances in marine sedimentary rocks spanning the past 3.5 billion years. We find evidence for relatively low authigenic phosphorus burial in shallow marine environments until about 800 to 700 million years ago. Our interpretation of the database leads us to propose that limited marginal phosphorus burial before that time was linked to phosphorus biolimitation, resulting in elemental stoichiometries in primary producers that diverged strongly from the Redfield ratio (the atomic ratio of carbon, nitrogen and phosphorus found in phytoplankton). We place our phosphorus record in a quantitative biogeochemical model framework and find that a combination of enhanced phosphorus scavenging in anoxic, iron-rich oceans and a nutrient-based bistability in atmospheric oxygen levels could have resulted in a stable low-oxygen world. The combination of these factors may explain the protracted oxygenation of Earth’s surface over the last 3.5 billion years of Earth history. However, our analysis also suggests that a fundamental shift in the phosphorus cycle may have occurred during the late Proterozoic eon (between 800 and 635 million years ago), coincident with a previously inferred shift in marine redox states, severe perturbations to Earth’s climate system, and the emergence of animals.

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.

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.

Field- and Lab-Based Potentiometric Titrations of Microbial Mats from the Fairmont Hot Spring, Canada

ABSTRACT Potentiometric titrations are an effective tool to constrain the protonation constants and site concentrations for microbial surface ligands. Protonation models developed from these experiments are often coupled with data from metal adsorption experiments to calculate microbial ligand-metal binding constants. Ultimately, the resulting surface complexation models can be used to predict metal immobilization behavior across diverse chemical conditions. However, most protonation and metal-ligand thermodynamic constants have been generated in laboratory experiments that use cultured microbes which may differ in their chemical reactivity from environmental samples. In this study, we investigate the use of in situ field potentiometric titrations of microbial mats at a carbonate hot spring located at Fairmont Hot Springs, British Columbia, with the aim to study microbial reactivities in a natural field system. We found that authigenic carbonate minerals complicated the potentiometric titration process due to a “carbonate spike” introduced by the contribution of inorganic carbonate mineral dissolution and subsequent carbonate speciation changes during the transition from low to high pH. This inhibits the determination of microbial surface ligand variety and concentrations. Our preliminary study also highlights the need for developing novel probes to quantify in situ microbial mat reactivity in future field investigations.

Phytoplankton contributions to the trace-element composition of Precambrian banded iron formations

Banded iron formations are economically important sedimentary deposits in Earth’s Precambrian rock record, consisting of alternating iron-rich (hematite, magnetite, and siderite) and silicate/carbonate (quartz, claylike minerals, dolomite, and ankerite) layers. Based on chemical analyses from banded iron formation units of the 2.48 Ga Dales Gorge Member of the Hamersley Group in Western Australia, it has been previously suggested that most, if not all, of the iron in banded iron formations could have been oxidized by anoxygenic phototrophic bacteria (photoferrotrophs) at cell densities considerably less than those found in modern iron-rich aqueous environments. However, oxygen-producing phytoplankton may have also been capable of supplying the necessary oxidizing power. Here, we revisit the question of the anoxygenic and oxygenic phytoplankton populations necessary to account for banded iron formation deposition and quantify the amount of selected trace elements (P, Mn, Co, Ni, Cu, Zn, Mo, Cd) that could have been associated with their biomass. Using an expanded geochemical data set for the Dales Gorge Member as an example, we

Earth’s youngest banded iron formation implies ferruginous conditions in the Early Cambrian ocean

It has been proposed that anoxic and iron-rich (ferruginous) marine conditions were common through most of Earth history. This view represents a major shift in our understanding of the evolution of marine chemistry. However, thus far, evidence for ferruginous conditions comes predominantly from Fe-speciation data. Given debate over these records, new evidence for Fe-rich marine conditions is a requisite if we are to shift our view regarding evolution of the marine redox landscape. Here we present strong evidence for ferruginous conditions by describing a suite of Fe-rich chemical sedimentary rocks—banded iron formation (BIF)—-deposited during the Early Cambrian in western China. Specifically, we provide new U-Pb geochronological data that confirm a depositional age of ca. 527 Ma for this unit, as well as rare earth element (REE) data are consistent with anoxic deposition. Similar to many Algoma-type Precambrian iron formations, these Early Cambrian sediments precipitated in a back-arc rift basin setting, where hydrothermally sourced iron drove the deposition of a BIF-like protolith, the youngest ever reported of regional extent without direct links to volcanogenic massive sulphide (VMS) deposits. Their presence indicates that marine environments were still characterized by chemical- and redox-stratification, thus supporting the view that—despite a dearth of modern marine analogues—ferruginous conditions continued to locally be a feature of early Phanerozoic seawater.