Nitrogen forms an integral part of the main building blocks of life, including DNA, RNA, and proteins. N2 is the dominant gas in Earth's atmosphere, and nitrogen is stored in all of Earth's ...geological reservoirs, including the crust, the mantle, and the core. As such, nitrogen geochemistry is fundamental to the evolution of planet Earth and the life it supports. Despite the importance of nitrogen in the Earth system, large gaps remain in our knowledge of how the surface and deep nitrogen cycles have evolved over geologic time. Here, we discuss the current understanding (or lack thereof) for how the unique interaction of biological innovation, geodynamics, and mantle petrology has acted to regulate Earth's nitrogen cycle over geologic timescales. In particular, we explore how temporal variations in the external (biosphere and atmosphere) and internal (crust and mantle) nitrogen cycles could have regulated atmospheric pN2. We consider three potential scenarios for the evolution of the geobiological nitrogen cycle over Earth's history: two in which atmospheric pN2 has changed unidirectionally (increased or decreased) over geologic time and one in which pN2 could have taken a dramatic deflection following the Great Oxidation Event. It is impossible to discriminate between these scenarios with the currently available models and datasets. However, we are optimistic that this problem can be solved, following a sustained, open‐minded, and multidisciplinary effort between surface and deep Earth communities.
Major changes in atmospheric and ocean chemistry occurred in the Paleoproterozoic era (2.5 to 1.6 billion years ago). Increasing oxidation dramatically changed Earth's surface, but few quantitative ...constraints exist on this important transition. This study describes the sedimentology, mineralogy, and geochemistry of a 2-billion-year-old, ~800-meter-thick evaporite succession from the Onega Basin in Russian Karelia. The deposit consists of a basal unit dominated by halite (~100 meters) followed by units dominated by anhydrite-magnesite (~500 meters) and dolomite-magnesite (~200 meters). The evaporite minerals robustly constrain marine sulfate concentrations to at least 10 millimoles per kilogram of water, representing an oxidant reservoir equivalent to more than 20% of the modern ocean-atmosphere oxidizing capacity. These results show that substantial amounts of surface oxidant accumulated during this critical transition in Earth's oxygenation.
Multiple sulphur (S) isotope ratios are powerful proxies to understand the complexity of S biogeochemical cycling through Deep Time. The disappearance of a sulphur mass‐independent fractionation ...(S‐MIF) signal in rocks <~2.4 Ga has been used to date a dramatic rise in atmospheric oxygen levels. However, intricacies of the S‐cycle before the Great Oxidation Event remain poorly understood. For example, the isotope composition of coeval atmospherically derived sulphur species is still debated. Furthermore, variation in Archaean pyrite δ34S values has been widely attributed to microbial sulphate reduction (MSR). While petrographic evidence for Archaean early‐diagenetic pyrite formation is common, textural evidence for the presence and distribution of MSR remains enigmatic. We combined detailed petrographic and in situ, high‐resolution multiple S‐isotope studies (δ34S and Δ33S) using secondary ion mass spectrometry (SIMS) to document the S‐isotope signatures of exceptionally well‐preserved, pyritised microbialites in shales from the ~2.65‐Ga Lokammona Formation, Ghaap Group, South Africa. The presence of MSR in this Neoarchaean microbial mat is supported by typical biogenic textures including wavy crinkled laminae, and early‐diagenetic pyrite containing <26‰ μm‐scale variations in δ34S and Δ33S = −0.21 ± 0.65‰ (±1σ). These large variations in δ34S values suggest Rayleigh distillation of a limited sulphate pool during high rates of MSR. Furthermore, we identified a second, morphologically distinct pyrite phase that precipitated after lithification, with δ34S = 8.36 ± 1.16‰ and Δ33S = 5.54 ± 1.53‰ (±1σ). We propose that the S‐MIF signature of this secondary pyrite does not reflect contemporaneous atmospheric processes at the time of deposition; instead, it formed by the influx of later‐stage sulphur‐bearing fluids containing an inherited atmospheric S‐MIF signal and/or from magnetic isotope effects during thermochemical sulphate reduction. These insights highlight the complementary nature of petrography and SIMS studies to resolve multigenerational pyrite formation pathways in the geological record.
Stable isotope compositions of biologically cycled elements encode information about the interaction between life and environment. On Earth, geochemical biomarkers have been used to probe the extent, ...nature, and activity of modern and ancient organisms. However, extracting biological information from stable isotopic compositions requires untangling the interconnected nature of the Earth’s biogeochemical system, and must be viewed through the lens of evolving metabolisms on an evolving planet. In this chapter, we provide an introduction to isotope geobiology and to the geobiological history of Earth. We discuss the isotope biogeochemistry of the biologically essential elements carbon, nitrogen and sulfur, and we summarize their distribution on the modern Earth as an interconnected network of isotopically fractionated reservoirs with contrasting residence times. We show how this framework can be used to explore the evolution of life and environments on the ancient Earth, which is our closest accessible analogue for an extraterrestrial planet.
We measured the δ98Mo of cells and media from molybdenum (Mo) assimilation experiments with the freshwater cyanobacterium Anabaena variabilis, grown with nitrate as a nitrogen (N) source or fixing ...atmospheric N2. This organism uses a Mo‐based nitrate reductase during nitrate utilization and a Mo‐based dinitrogenase during N2 fixation under culture conditions here. We also demonstrate that it has a high‐affinity Mo uptake system (ModABC) similar to other cyanobacteria, including marine N2‐fixing strains. Anabaena variabilis preferentially assimilated light isotopes of Mo in all experiments, resulting in fractionations of −0.2‰ to −1.0‰ ± 0.2‰ between cells and media (εcells–media), extending the range of biological Mo fractionations previously reported. The fractionations were internally consistent within experiments, but varied with the N source utilized and for different growth phases sampled. During growth on nitrate, A. variabilis consistently produced fractionations of −0.3 ± 0.1‰ (mean ± standard deviation between experiments). When fixing N2, A. variabilis produced fractionations of −0.9 ± 0.1‰ during exponential growth, and −0.5 ± 0.1‰ during stationary phase. This pattern is inconsistent with a simple kinetic isotope effect associated with Mo transport, because Mo is likely transported through the ModABC uptake system under all conditions studied. We present a reaction network model for Mo isotope fractionation that demonstrates how Mo transport and storage, coordination changes during enzymatic incorporation, and the distribution of Mo inside the cell could all contribute to the total biological fractionations. Additionally, we discuss the potential importance of biologically incorporated Mo to organic matter‐bound Mo in marine sediments.
Models of language production must account for how speakers select referential expressions, a process that is complicated by the range of options available to speakers (e.g. he, Pim, Dr. Levelt). ...This paper reviews models of reference production, and suggests that they fall into two classes: (1) Pragmatic selection models, and (2) Rational models. We review evidence for and against each class of model, focusing on the use of pronouns. We argue that pronoun selection is not primarily driven by considerations of efficiency, and current models of accessibility do not explain the range of variation in production choices. We identify several challenges for future work in this area.
We measured the δ⁹⁸Mo of cells and media from molybdenum (Mo) assimilation experiments with the freshwater cyanobacterium Anabaena variabilis, grown with nitrate as a nitrogen (N) source or fixing ...atmospheric N₂. This organism uses a Mo-based nitrate reductase during nitrate utilization and a Mo-based dinitrogenase during N₂ fixation under culture conditions here. We also demonstrate that it has a high-affinity Mo uptake system (ModABC) similar to other cyanobacteria, including marine N₂-fixing strains. Anabaena variabilis preferentially assimilated light isotopes of Mo in all experiments, resulting in fractionations of -0.2‰ to -1.0‰ ± 0.2‰ between cells and media (ε(cells-media)), extending the range of biological Mo fractionations previously reported. The fractionations were internally consistent within experiments, but varied with the N source utilized and for different growth phases sampled. During growth on nitrate, A. variabilis consistently produced fractionations of -0.3 ± 0.1‰ (mean ± standard deviation between experiments). When fixing N₂, A. variabilis produced fractionations of -0.9 ± 0.1‰ during exponential growth, and -0.5 ± 0.1‰ during stationary phase. This pattern is inconsistent with a simple kinetic isotope effect associated with Mo transport, because Mo is likely transported through the ModABC uptake system under all conditions studied. We present a reaction network model for Mo isotope fractionation that demonstrates how Mo transport and storage, coordination changes during enzymatic incorporation, and the distribution of Mo inside the cell could all contribute to the total biological fractionations. Additionally, we discuss the potential importance of biologically incorporated Mo to organic matter-bound Mo in marine sediments.
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