Nitrogen isotopes in deep time

Nitrogen is an essential nutrient for life, and its sources and cycling have varied over earth history. Stable isotope ratios of nitrogen compounds (expressed as δ15N, in ‰) are preserved in the sedimentary record and track these changes, providing important insights into associated biogeochemical feedbacks. Here we review the use of nitrogen stable isotope geochemistry in unravelling the evolution of the global N cycle in deep time. We highlight difficulties with preservation, unambiguous interpretations, and local versus global effects. We end with several case studies illustrating how depositional and stratigraphic context is crucial in reliably interpreting δ15N records in ancient marine sediments, both in ancient anoxic (Archean) and more recent well oxygenated (Phanerozoic) environments.Postprin

Biogeodynamics : bridging the gap between surface and deep Earth processes

Life is sustained by a critical and not insubstantial set of elements, nearly all of which are contained within large rock reservoirs and cycled between Earth's surface and the mantle via subduction zone plate tectonics. Over geologic time scales, plate tectonics plays a critical role in recycling subducted bioactive elements lost to the mantle back to the ocean–biosphere system, via outgassing and volcanism. Biology additionally relies on tectonic processes to supply rock-bound ‘nutrients’ to marine and terrestrial ecosystems via uplift and erosion. Thus, the development of modern-style plate tectonics and the generation of stable continents were key events in the evolution of the biosphere on Earth, and similar tectonic processes could be crucial for the development of habitability on exoplanets. Despite this vital ‘biogeodynamic’ connection, directly testing hypotheses about feedbacks between the deep Earth and the biosphere remains challenging. Here, I discuss potential avenues to bridge the biosphere–geosphere gap, focusing specifically on the global cycling and bioavailability of major nutrients (nitrogen and phosphorus) over geologic time scales.PostprintPeer reviewe

Redox State of the Neoarchean Earth Environment

A Titan-like organic haze has been hypothesized for Earth's atmosphere prior to widespread surface oxygenation approx.2.45 billion years ago (Ga). We present a high-resolution record of quadruple sulfur isotopes, carbon isotopes, and Fe speciation from the approx.2.65-2.5 Ga Ghaap Group, South Africa, which suggest a linkage between organic haze and the biogeochemical cycling of carbon, sulfur, oxygen, and iron on the Archean Earth. These sediments provide evidence for oxygen production in microbial mats and localized oxygenation of surface waters. However, this oxygen production occurred under a reduced atmosphere which existed in multiple distinct redox states that correlate to changes in carbon and sulfur isotopes. The data are corroborated by photochemical model results that suggest bi-stable transitions between organic haze and haze-free atmospheric conditions in the Archean. These geochemical correlations also extend to other datasets, indicating that variations in the character of anomalous sulfur fractionation could provide insight into the role of carbon-bearing species in the reducing Archean atmosphere

Nitrates as a potential N Supply for microbial ecosystems in a hyperarid Mars analog system

This research was funded by European Research Council (ERC) under the European Union’s Horizon 2020 Research and Innovation Programme (Grant Agreement 678812) (to M.W.C.). J.S. also acknowledges support from the China Scholarship Council (CSC).Nitrate is common in Mars sediments owing to long-term atmospheric photolysis, oxidation, and potentially, impact shock heating. The Atacama Desert in Chile, which is the driest region on Earth and rich in nitrate deposits, is used as a Mars analog in this study to explore the potential effects of high nitrate levels on growth of extremophilic ecosystems. Seven study sites sampled across an aridity gradient in the Atacama Desert were categorized into 3 clusters—hyperarid, middle, and arid sites—as defined by essential soil physical and chemical properties. Intriguingly, the distribution of nitrate concentrations in the shallow subsurface suggests that the buildup of nitrate is not solely controlled by precipitation. Correlations of nitrate with SiO2/Al2O3 and grain sizes suggest that sedimentation rates may also be important in controlling nitrate distribution. At arid sites receiving more than 10 mm/yr precipitation, rainfall shows a stronger impact on biomass than nitrate does. However, high nitrate to organic carbon ratios are generally beneficial to N assimilation, as evidenced both by soil geochemistry and enriched culturing experiments. This study suggests that even in the absence of precipitation, nitrate levels on a more recent, hyperarid Mars could be sufficiently high to benefit potentially extant Martian microorganisms.Publisher PDFPeer reviewe

Anaerobic nitrogen cycling on a Neoarchean ocean margin

This study was supported financially by NERC Fellowship NE/H016805/2 (to AZ), NERC Standard Grant NE/J023485/2 (to AZ and MC), NSF EAR-1455258 (to CKJ).A persistently aerobic marine nitrogen cycle featuring the biologically mediated oxidation of ammonium to nitrate has likely been in place since the Great Oxidation Event (GOE) some 2.3 billion years ago. Although nitrogen isotope data from some Neoarchaean sediments suggests transient nitrate availability prior to the GOE, these data are open to other interpretations. This is especially so as these data come from relatively deep-water environments that were spatially divorced from shallow-water settings that were the most likely sites for the accumulation of oxygen and the generation of nitrate. Here we present the first nitrogen isotope data from contemporaneous shallow-water sediments to constrain the nitrogen cycle in shallow Late Archaean settings. The BH-1 Sacha core through the Campbellrand-Malmani carbonate platform records a transition from a shallow siliciclastic/carbonate ramp to a rimmed carbonate shelf with the potential for reduced communication with the open ocean. In these settings nitrogen isotope δ15N data from sub- to peri-tidal and lagoonal settings are close to 0‰, indicating diazotrophy or the complete utilization of remineralised ammonium with an isotopic composition of near 0‰. Our dataset also includes negative δ15N values that suggest the presence of an ammonium pool of concentrations sufficient to have allowed for non-quantitative assimilation. We suggest that this condition may have been the result of upwelling of phosphorus-rich deep waters into the photic zone, stimulating primary productivity and creating an enhanced flux of organic matter that was subsequently remineralised and persisted in the dominantly anoxic Neoarchaean marine environment. Notably, we find only limited evidence of coupled nitrification/denitrification, even in these shallow water environments, calling into question previous suggestions that the Late Archaean nitrogen cycle was characterized by widespread aerobic nitrogen cycling. Rather, aerobic nitrogen cycling was likely spatially heterogeneous and tied to loci of high oxygen production while zones of shallow water anoxia persisted.PostprintPeer reviewe

A copper isotope investigation of methane cycling in Late Archaean sediments

This research was supported by NERC award NE/L002590/1 to the IAPETUS DTP, and by NERC Standard Grant NE/J023485/2 to A.L.Z. The initiation of Cu isotope analysis at the University of St Andrews was aided significantly by a Carnegie Trust Research Incentive Grant awarded to P.S.S.The rise of oxygenic photosynthesis arguably represents the most important evolutionary step in Earth history. Recent studies, however, suggest that Earth’s pre-oxidative atmosphere was also heavily influenced by biological feedbacks. Most notably, recent geochemical records propose the existence of a hydrocarbon haze which periodically formed in response to enhanced biospheric methane fluxes. Copper isotopes provide a potential proxy for biological methane cycling; Cu is a bioessential trace metal and a key element in the aerobic oxidation of methane to carbon dioxide (methanotrophy). In addition, Cu isotopes are fractionated during biological uptake. Here, we present a high-resolution Cu isotope record measured in a suite of shales and carbonates from core GKF01, through the ~2.6–2.5 Ga Campbellrand-Malmani carbonate platform. Our data show a 0.85‰ range in Cu isotope composition and a negative excursion that predates the onset of a haze event. We interpret this excursion as representing a period of enhanced aerobic methane oxidation before the onset of the Great Oxidation Event. This places valuable time constraints on the evolution of this metabolism and firmly establishing Cu isotopes as a biomarker in Late Archaean rocks.PostprintPeer reviewe

Sulfur isotopes of hydrothermal vent fossils and insights into microbial sulfur cycling within a lower Paleozoic (Ordovician‐early Silurian) vent community

This study was supported by a UK Natural Environment Research Council grant (NERC; number NE/R000670/1 to AG). MG is also grateful for support from an Ifremer Postdoctoral Fellowship. Alvinella samples were collected with the help of a NERC Small Grant (number NE/C000714/1 to CTSL). S isotopic analyses were undertaken under NERC Facility awards IP-1755-1117 and IMF672/1118.Symbioses between metazoans and microbes involved in sulfur cycling are integral to the ability of animals to thrive within deep‐sea hydrothermal vent environments; the development of such interactions is regarded as a key adaptation in enabling animals to successfully colonize vents. Microbes often colonize the surfaces of vent animals and, remarkably, these associations can also be observed intricately preserved by pyrite in the fossil record of vent environments, stretching back to the lower Paleozoic (Ordovician‐early Silurian). In non‐vent environments, sulfur isotopes are often employed to investigate the metabolic strategies of both modern and fossil organisms, as certain metabolic pathways of microbes, notably sulfate reduction, can produce large sulfur isotope fractionations. However, the sulfur isotopes of vent fossils, both ancient and recently mineralized, have seldom been explored, and it is not known if the pyrite‐preserved vent organisms might also preserve potential signatures of their metabolisms. Here, we use high‐resolution secondary ion mass spectrometry (SIMS) to investigate the sulfur isotopes of pyrites from recently mineralized and Ordovician‐early Silurian tubeworm fossils with associated microbial fossils. Our results demonstrate that pyrites containing microbial fossils consistently have significantly more negative δ34S values compared with nearby non‐fossiliferous pyrites, and thus represent the first indication that the presence of microbial sulfur‐cycling communities active at the time of pyrite formation influenced the sulfur isotope signatures of pyrite at hydrothermal vents. The observed depletions in δ34S are generally small in magnitude and are perhaps best explained by sulfur isotope fractionation through a combination of sulfur‐cycling processes carried out by vent microbes. These results highlight the potential for using sulfur isotopes to explore biological functional relationships within fossil vent communities, and to enhance understanding of how microbial and animal life has co‐evolved to colonize vents throughout geological time.Publisher PDFPeer reviewe

Mantle sources and magma evolution in Europe's largest rare earth element belt (Gardar Province, SW Greenland) : new insights from sulfur isotopes

This work is a contribution to the HiTech AlkCarb project and was funded by the European Union's Horizon 2020 research and innovation programme under grant agreement No. 689909. W.H. also acknowledges support from a UKRI Future Leaders Fellowship (MR/S033505/1). A.J.B. is funded by the NERC National Environment Isotope Facility award (NE/S011587/1) and the Scottish Universities Environmental Research Centre.Alkaline igneous complexes are often rich in rare earth elements (REE) and other metals essential for modern technologies. Although a variety of magmatic and hydrothermal processes explain the occurrence of individual deposits, one common feature identified in almost all studies, is a REE-enriched parental melt sourced from the lithospheric mantle. Fundamental questions remain about the origin and importance of the mantle source in the genesis of REE-rich magmas. In particular, it is often unclear whether localized enrichments within an alkaline province reflect heterogeneity in the mantle source lithology (caused by prior subduction or plume activity) or variations in the degree of partial melting and differentiation of a largely homogeneous source. Sulfur isotopes offer a means of testing these hypotheses because they are unaffected by high temperature partial melting processes and can fingerprint different mantle sources. Although one must be careful to rule out subsequent isotope fractionation during magma ascent, degassing and crustal interactions. Here, we present new S concentration and isotope (δ34S) measurements, as well as a compilation of major and trace element data, for a suite of alkaline magmatic units and crustal lithologies from the Mesoproterozoic Gardar Province. Samples span all phases of Gardar magmatism (1330–1140 Ma) and include regional dykes, rift lavas and the alkaline complexes Motzfeldt and Ilímaussaq, which represent two of Europe's largest REE deposits. We show that the vast majority of our 115 samples have S contents >100 ppm and δ34S of −1 to 5‰. Only 8 samples (with low S contents, <100 ppm) show evidence for crustal interactions, implying that the vast majority of Gardar melts preserve the S isotopic signature of their magma source. Importantly, samples from across the Gardar Province δ34S have above the canonical mantle range (≤−1.4‰) and therefore require recycled surface S in their mantle source. Elevated values are explained by a period of Andean-style subduction and mantle metasomatism which took place ∼500 Ma before rift onset and are also supported by trace elements signatures (e.g. Ba/La) which match modern subduction zones. Comparing the various generations of Gardar magmas, we find that δ34S  values, large ion lithophile elements (K, Ba, P) and selective incompatible elements (Nb and light REE) are particularly enriched in the Late Gardar dykes, alkaline complexes and clusters of silica-undersaturated dykes spatially associated with the alkaline complexes. These data indicate that subduction-related metasomatism of the Gardar mantle was spatially heterogeneous, and that alkaline complexes are sourced from localized mantle domains highly enriched in 34S, REE, alkalis and volatiles (particularly, F). Since alkalis and volatiles play an essential role in driving extreme differentiation of alkaline melts and fluids, we suggest the co-location of these species plus incompatible metals at high concentrations in the lithospheric mantle is a critical first-step in the genesis of a world-class alkaline REE deposit. S isotopes are powerful tools for identifying enriched mantle domains and the sources of mineralized alkaline igneous bodies.Publisher PDFPeer reviewe

Sulfate was a trace constituent of Archean seawater

In the low-oxygen Archean world (>2400 million years ago), seawater sulfate concentrations were much lower than today, yet open questions frustrate the translation of modern measurements of sulfur isotope fractionations into estimates of Archean seawater sulfate concentrations. In the water column of Lake Matano, Indonesia, a low-sulfate analog for the Archean ocean, we find large (>20 per mil) sulfur isotope fractionations between sulfate and sulfide, but the underlying sediment sulfides preserve a muted range of δ^(34)S values. Using models informed by sulfur cycling in Lake Matano, we infer Archean seawater sulfate concentrations of less than 2.5 micromolar. At these low concentrations, marine sulfate residence times were likely 10^3 to 10^4 years, and sulfate scarcity would have shaped early global biogeochemical cycles, possibly restricting biological productivity in Archean oceans

Origin and evolution of the atmospheres of early Venus, Earth and Mars

We review the origin and evolution of the atmospheres of Earth, Venus and Mars from the time when their accreting bodies were released from the protoplanetary disk a few million years after the origin of the Sun. If the accreting planetary cores reached masses ≥0.5 MEarth before the gas in the disk disappeared, primordial atmospheres consisting mainly of H2 form around the young planetary body, contrary to late-stage planet formation, where terrestrial planets accrete material after the nebula phase of the disk. The differences between these two scenarios are explored by investigating non-radiogenic atmospheric noble gas isotope anomalies observed on the three terrestrial planets. The role of the young Sun’s more efficient EUV radiation and of the plasma environment into the escape of early atmospheres is also addressed. We discuss the catastrophic outgassing of volatiles and the formation and cooling of steam atmospheres after the solidification of magma oceans and we describe the geochemical evidence for additional delivery of volatile-rich chondritic materials during the main stages of terrestrial planet formation. The evolution scenario of early Earth is then compared with the atmospheric evolution of planets where no active plate tectonics emerged like on Venus and Mars. We look at the diversity between early Earth, Venus and Mars, which is found to be related to their differing geochemical, geodynamical and geophysical conditions, including plate tectonics, crust and mantle oxidation processes and their involvement in degassing processes of secondary N2 atmospheres. The buildup of atmospheric N2, O2, and the role of greenhouse gases such as CO2 and CH4 to counter the Faint Young Sun Paradox (FYSP), when the earliest life forms on Earth originated until the Great Oxidation Event ≈ 2.3 Gyr ago, are addressed. This review concludes with a discussion on the implications of understanding Earth’s geophysical and related atmospheric evolution in relation to the discovery of potential habitable terrestrial exoplanets.PostprintPeer reviewe