Nitrogen in the Earth System: planetary budget and cycling during geologic history

The distribution and geologic history of nitrogen on Earth is poorly known. Traditionally thought to be an inert gas, with only a small but important biologic cycle, geochemical investigation highlights that it can also be present in rocks and minerals. Even at low concentrations, the great mass of the solid Earth allows for the possibility of substantial N mass and cycling in the geosphere over Earth history. Thus, the assumption that N on the surface of the Earth has remained in steady state over Earth history can be questioned. The research goals of this thesis are to investigate the Earth System N cycle using both large- and small-scale approaches. I present a comprehensive literature compilation to ascertain the N budget of Earth. Determining the total abundance of N in all reservoirs of the Earth, including the atmosphere, oceans, crust, mantle, and core is crucial to a discussion of its cycling in the past. This budget study suggests that the majority of planetary N is likely in the core, with the Bulk Silicate Earth a more massive reservoir than the atmosphere. I also present experimental data and data from lunar samples as added context. As quantification of geologic N is difficult, I present research detailing the adaptation of a fluorometric technique common in aquatic geochemistry for use on geologic samples. I compare fluorometry analysis of geochemical standards to several other techniques: colourimetry, elemental analyzer mass spectrometry, and neutron activation analysis. Fluorometry generally behaves well for crystalline samples, and is a relatively quick and easy alternative to more expensive or intensive techniques. As a preliminary application, I have determined a N budget estimate for the continental crust based on analysis of crystalline crustal rocks and glacial tills from North America. This budget is consistent with published work, suggesting about 2 × 1018 kg N, or half a present atmospheric mass of N, is in the continental crust. I also present a geochemical study measuring N-isotopes and redox sensitive trace elements from a syn-glacial unit deposited during the the Marinoan Snowball Earth. Snowball Earth events were the most extreme glaciations in Earth history. The measurements presented herein are the first to quantify biologic activity via N-isotopes as well as the redox state of the atmosphere and ocean using trace elements from this intriguing time period in Earth history. The data suggests that there was active N- fixing in the biosphere, persistent but limited O2, nitrification, and nearly quantitative denitrification during the glaciation. After the glacial interval, O2 levels increased and denitrification levels dropped, indicated by near-modern δ15N values. The combined use of N-isotope with redox sensitive trace elements provides a more nuanced and comprehensive view in reconstructing past ocean and biologic conditions. Lastly, I present an Earth-system N cycle model with nominal results. Previous modelling efforts have agreed with the traditional notion that atmospheric N-levels have remained constant over geologic time. This is in contrast with modern geochemical evidence suggesting net transport of N from the surface into the mantle. The aim, in turn, of this model is to model N cycling over Earth history by explicitly incorporating both biologic and geologic fluxes. The model is driven by a mantle cooling history and calculated plate tectonic speed, as well as a prescribed atmospheric O2 evolution history. This approach is the first of its kind, to my knowledge, and produces stable model runs over Earth history. While tuning and sensitivity studies may be required for publishable results, nominal runs are compelling. In model output, atmospheric N varies by an factor of 2 − 3 over Earth history, and the availability of nutrients (i.e., PO4) exerts a strong control on biologic activity and movement of N throughout the Earth system. Such a planetary perspective on N serves as an entry point into discussions of planetary evolution as a whole. With the great increase in the number of discovered exoplanets, the scientific community is charged with developing models of planetary evolution and factors that promote habitability. Comparison of Earth to its solar system neighbours and future data on exoplanets will allow a system of evolution pathways to be explored, with the role of N expected to be prominent in discussions of habitability and planetary evolution.

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