Hydrothermal Regeneration of Ammonium as a Basin-Scale Driver of Primary Productivity.

Hydrothermal vents are important targets in the search for life on other planets due to their potential to generate key catalytic surfaces and organic compounds for biogenesis. Less well studied, however, is the role of hydrothermal circulation in maintaining a biosphere beyond its origin. In this study, we explored this question with analyses of organic carbon, nitrogen abundances, and isotopic ratios from the Paleoproterozoic Zaonega Formation (2.0 Ga), NW Russia, which is composed of interbedded sedimentary and mafic igneous rocks. Previous studies have documented mobilization of hydrocarbons, likely associated with magmatic intrusions into unconsolidated sediments. The igneous bodies are extensively hydrothermally altered. Our data reveal strong nitrogen enrichments of up to 0.6 wt % in these altered igneous rocks, suggesting that the hydrothermal fluids carried ammonium concentrations in the millimolar range, which is consistent with some modern hydrothermal vents. Furthermore, large isotopic offsets of ∼10‰ between organic-bound and silicate-bound nitrogen are most parsimoniously explained by partial biological uptake of ammonium from the vent fluid. Our results, therefore, show that hydrothermal activity in ancient marine basins could provide a locally high flux of recycled nitrogen. Hydrothermal nutrient recycling may thus be an important mechanism for maintaining a large biosphere on anoxic worlds.

Diagenetic nutrient supplies to the Proterozoic biosphere archived in divergent nitrogen isotopic ratios between kerogen and silicate minerals.

Nitrogen isotopes and abundances in sedimentary rocks have become an important tool for reconstructing biogeochemical cycles in ancient ecosystems. There are two archives of nitrogen in the rock record, namely kerogen-bound amines and silicate-bound ammonium, and it is well documented that the isotopic ratios of these two archives can be offset from one another. This offset has been observed to increase with metamorphic grade, suggesting that it may be related to the bonding environment in differing nitrogen host phases and associated equilibrium isotope fractionation. However, theoretical bounds for this effect have not been established, and it remains possible that some isotopic offsets predate metamorphism. In support of this hypothesis, we report an unexpectedly large isotopic offset of 4-5‰ in siltstones of very low metamorphic grade from the late Mesoproterozoic Diabaig Formation in NW Scotland (1.0 Ga). Carbon to nitrogen ratios of bulk rocks are 2-3 times lower than in other Mesoproterozoic sections. The rocks also contain early-formed phosphate concretions and display wrinkled surfaces on bedding planes, indicative of fossilised microbial mats. Collectively, these data are most parsimoniously interpreted as evidence of diagenetic ammonium release from microbial mats into porewaters, followed by partial oxidation to nitrite or nitrate at the sediment-water interface. This process would render residual ammonium in clays isotopically heavy, while the resulting nitrite or nitrate would be relatively lighter and captured in new biomass, leading to the observed isotopic divergence. The same diagenetic degradation pathway likely also liberated phosphate that was trapped within concretions. Diagenetic release of nutrients is known to occur in modern settings, and our data suggest that nitrogen isotopes may be a way to track this local sedimentary nutrient source in past environments. Lastly, we speculate that diagenetic nutrient recycling within Proterozoic microbial mats may have created a favourable niche for eukaryotic organisms in shallow waters.

The Great Oxidation Event preceded a Paleoproterozoic "snowball Earth".

The inability to resolve the exact temporal relationship between two pivotal events in Earth history, the Paleoproterozoic Great Oxidation Event (GOE) and the first "snowball Earth" global glaciation, has precluded assessing causality between changing atmospheric composition and ancient climate change. Here we present temporally resolved quadruple sulfur isotope measurements (δ34S, ∆33S, and ∆36S) from the Paleoproterozoic Seidorechka and Polisarka Sedimentary Formations on the Fennoscandian Shield, northwest Russia, that address this issue. Sulfides in the former preserve evidence of mass-independent fractionation of sulfur isotopes (S-MIF) falling within uncertainty of the Archean reference array with a ∆36S/∆33S slope of -1.8 and have small negative ∆33S values, whereas in the latter mass-dependent fractionation of sulfur isotopes (S-MDF) is evident, with a ∆36S/∆33S slope of -8.8. These trends, combined with geochronological constraints, place the S-MIF/S-MDF transition, the key indicator of the GOE, between 2,501.5 ± 1.7 Ma and 2,434 ± 6.6 Ma. These are the tightest temporal and stratigraphic constraints yet for the S-MIF/S-MDF transition and show that its timing in Fennoscandia is consistent with the S-MIF/S-MDF transition in North America and South Africa. Further, the glacigenic part of the Polisarka Formation occurs 60 m above the sedimentary succession containing S-MDF signals. Hence, our findings confirm unambiguously that the S-MIF/S-MDF transition preceded the Paleoproterozoic snowball Earth. Resolution of this temporal relationship constrains cause-and-effect drivers of Earth's oxygenation, specifically ruling out conceptual models in which global glaciation precedes or causes the evolution of oxygenic photosynthesis.