Triple oxygen isotope evidence for limited mid-Proterozoic primary productivity.

The global biosphere is commonly assumed to have been less productive before the rise of complex eukaryotic ecosystems than it is today1. However, direct evidence for this assertion is lacking. Here we present triple oxygen isotope measurements (∆17O) from sedimentary sulfates from the Sibley basin (Ontario, Canada) dated to about 1.4 billion years ago, which provide evidence for a less productive biosphere in the middle of the Proterozoic eon. We report what are, to our knowledge, the most-negative ∆17O values (down to -0.88‰) observed in sulfates, except for those from the terminal Cryogenian period2. This observation demonstrates that the mid-Proterozoic atmosphere was distinct from what persisted over approximately the past 0.5 billion years, directly reflecting a unique interplay among the atmospheric partial pressures of CO2 and O2 and the photosynthetic O2 flux at this time3. Oxygenic gross primary productivity is stoichiometrically related to the photosynthetic O2 flux to the atmosphere. Under current estimates of mid-Proterozoic atmospheric partial pressure of CO2 (2-30 times that of pre-anthropogenic levels), our modelling indicates that gross primary productivity was between about 6% and 41% of pre-anthropogenic levels if atmospheric O2 was between 0.1-1% or 1-10% of pre-anthropogenic levels, respectively. When compared to estimates of Archaean4-6 and Phanerozoic primary production7, these model solutions show that an increasingly more productive biosphere accompanied the broad secular pattern of increasing atmospheric O2 over geologic time8.

The paleoredox context of early eukaryotic evolution: insights from the Tonian Mackenzie Mountains Supergroup, Canada.

Tonian (ca. 1000-720 Ma) marine environments are hypothesised to have experienced major redox changes coinciding with the evolution and diversification of multicellular eukaryotes. In particular, the earliest Tonian stratigraphic record features the colonisation of benthic habitats by multicellular macroscopic algae, which would have been powerful ecosystem engineers that contributed to the oxygenation of the oceans and the reorganisation of biogeochemical cycles. However, the paleoredox context of this expansion of macroalgal habitats in Tonian nearshore marine environments remains uncertain due to limited well-preserved fossils and stratigraphy. As such, the interdependent relationship between early complex life and ocean redox state is unclear. An assemblage of macrofossils including the chlorophyte macroalga Archaeochaeta guncho was recently discovered in the lower Mackenzie Mountains Supergroup in Yukon (Canada), which archives marine sedimentation from ca. 950-775 Ma, permitting investigation into environmental evolution coincident with eukaryotic ecosystem evolution and expansion. Here we present multi-proxy geochemical data from the lower Mackenzie Mountains Supergroup to constrain the paleoredox environment within which these large benthic macroalgae thrived. Two transects show evidence for basin-wide anoxic (ferruginous) oceanic conditions (i.e., high FeHR/FeT, low Fepy/FeHR), with muted redox-sensitive trace metal enrichments and possible seasonal variability. However, the weathering of sulfide minerals in the studied samples may obscure geochemical signatures of euxinic conditions. These results suggest that macroalgae colonized shallow environments in an ocean that remained dominantly anoxic with limited evidence for oxygenation until ca. 850 Ma. Collectively, these geochemical results provide novel insights into the environmental conditions surrounding the evolution and expansion of benthic macroalgae and the eventual dominance of oxygenated oceanic conditions required for the later emergence of animals.

Atmospheric sulfur is recycled to the crystalline continental crust during supercontinent formation.

The sulfur cycle across the lithosphere and the role of this volatile element in the metasomatism of the mantle at ancient cratonic boundaries are poorly constrained. We address these knowledge gaps by tracking the journey of sulfur in the assembly of a Proterozoic supercontinent using mass independent isotope fractionation (MIF-S) as an indelible tracer. MIF-S is a signature that was imparted to supracrustal sulfur reservoirs before the ~2.4 Ga Great Oxidation Event. The spatial representation of multiple sulfur isotope data indicates that successive Proterozoic granitoid suites preserve Δ33S up to +0.8‰ in areas adjacent to Archean cratons. These results indicate that suturing of cratons began with devolatilisation of slab-derived sediments deep in the lithosphere. This process transferred atmospheric sulfur to a mantle source reservoir, which was tapped intermittently for over 300 million years of magmatism. Our work tracks pathways and storage of sulfur in the lithosphere at craton margins.

Degassing-induced fractionation of multiple sulphur isotopes unveils post-Archaean recycled oceanic crust signal in hotspot lava.

Mantle source regions feeding hotspot volcanoes likely contain recycled subducted material. Anomalous sulphur (S) isotope signatures in hotspot lavas have tied ancient surface S to this deep geological cycle, but their potential modification by shallow magmatic processes has generally been overlooked. Here we present S isotope measurements in magmatic sulphides, silicate melt inclusions and matrix glasses from the recent eruption of a hotspot volcano at El Hierro, Canary Islands, which show that degassing induces strongly negative δ34S fractionation in both silicate and sulphide melts. Our results reflect the complex interplay among redox conditions, S speciation and degassing. The isotopic fractionation is mass dependent (Δ33S = 0‰), thus lacking evidence for the recycled Archaean crust signal recently identified at other hotspot volcanoes. However, the source has an enriched signature (δ34S ~ + 3‰), which supports the presence of younger 34S-rich recycled oceanic material in the Canary Island mantle plume.