Thematic Articles

Nitrogen in the Silicate Earth: Speciation and Isotopic Behavior during Mineral–Fluid Interactions

Nitrogen is the main constituent of Earth’s atmosphere and a key component of the biosphere, but it is a trace element in the major silicate reservoirs. The relatively low concentrations (parts per million level) complicate efforts to constrain the nitrogen speciation and abundance in the mantle and crust. In most silicates, nitrogen occurs as NH4 + (substituting for K+), whereas its speciation in hydrous fluids and silicate melts can vary widely depending in large part on redox conditions. Current knowledge of nitrogen isotope fractionation among relevant mineral and fluid/melt phases is limited by the lack of experimental data to confirm theoretical predictions of these fractionations. Modeling of modern and long-term nitrogen cycling on Earth will be advanced by better constraints on the sizes and isotopic compositions of the major crust and mantle nitrogen reservoirs.

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Biogeochemical Cycling of Nitrogen on the Early Earth

Variations in the nitrogen isotope composition of ancient organic matter and associated sediments provide clues for the early evolution of Earth’s atmosphere–ocean–biosphere system. In particular, large isotopic variations have been linked to the protracted oxygenation of Earth’s atmosphere during the Precambrian. Important problems being investigated include the nature of the variations observed at specifi c times in Earth’s history and the degree of preservation of ancient nitrogen biogeochemical signatures during diagenesis and metamorphism. Interpreting these records in Archean sedimentary environments and their possible implications for the evolution of Earth’s early atmosphere, ocean, and life is challenging.

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Stable Isotopes as Tracers of Anthropogenic Nitrogen Sources, Deposition, and Impacts

The global nitrogen cycle has been perturbed by human activities, including agriculture, land-use change, and fossil fuel burning. This perturbation ranges from the local to global scale, as anthropogenic reactive nitrogen can be transported over long distances in the atmosphere, in groundwater, and in stream networks and can even impact the open ocean. Stable isotope signatures characteristic of reactive nitrogen can be used to trace its deposition in the present day, as well as in the past. Here we focus on the use of stable isotopes to trace the sources, transport, and impacts of anthropogenic nitrogen in the modern nitrogen cycle.

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Nitrogen: Highly Volatile yet Surprisingly Compatible

Nitrogen exhibits an intriguing combination of highly volatile behavior (particularly as N2), appreciable reactivity, and surprising compatibility in the deep Earth. Nitrogen is incorporated into the biosphere and then, through diagenesis and low-grade metamorphism, is conveyed into the lithosphere and the deeper Earth. The investigation of N behavior in the biosphere, hydrosphere, and atmosphere has led to many important discoveries regarding biogeochemical pathways, including in areas such as trophic interactions and anthropogenic impacts on terrestrial and marine environments (e.g. nutrient pollution, eutrophication). Nitrogen can act as an excellent tracer of the transfer of sedimentary/organic materials into and within deep-Earth reservoirs and shows great potential as a tracer of life on early Earth and elsewhere in the Solar System.

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Formation and Exhumation of Ultrahigh-Pressure Terranes

The reigning paradigm for the formation and exhumation of continental ultrahigh-pressure (UHP) terranes is the subduction of crust to mantle depths and the return of crustal slices within the subduction channel— all at plate tectonic rates. Additional processes beyond the paradigm are needed to explain the diversity of geological observations gathered from the growing study of UHP terranes—for example, variations in the size, degree of deformation, petrologic evolution, timing of UHP metamorphism, and exhumation rates. Numerical models that evaluate physical parameters in time and space have produced new insights into the formation and exhumation of UHP terranes.

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Deep Fluids in Subducted Continental Crust

Establishing the timing and duration of ultrahigh-pressure metamorphism (UHP) for crustal rocks subducted to mantle depths of over 100 km requires high-precision geochronology directly coupled with pressure-sensitive indicators. The best links between UHP conditions and an age estimate are inclusions of the UHP indicator minerals coesite and/or diamond in datable zircon or garnet. Lu–Hf and Sm–Nd garnet ages define the prograde and peak portions of the pressure–temperature path for cold (<700 ºC), fast (>1 cm/y) UHP systems. UHP metamorphism in hotter (>800 ºC) and slower (<1 cm/y) terranes is best dated by U–Pb analysis of coesite-bearing zircon domains coupled with Sm–Nd and Lu–Hf garnet analysis.><1 cm/y) terranes is best dated by U–Pb analysis of coesite-bearing zircon domains coupled with Sm–Nd and Lu–Hf garnet analysis.

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Linking Time to the Pressure–Temperature Path for Ultrahigh-Pressure Rocks

Establishing the timing and duration of ultrahigh-pressure metamorphism (UHP) for crustal rocks subducted to mantle depths of over 100 km requires high-precision geochronology directly coupled with pressure-sensitive indicators. The best links between UHP conditions and an age estimate are inclusions of the UHP indicator minerals coesite and/or diamond in datable zircon or garnet. Lu–Hf and Sm–Nd garnet ages define the prograde and peak portions of the pressure–temperature path for cold (<700 ºC), fast (>1 cm/y) UHP systems. UHP metamorphism in hotter (>800 ºC) and slower (<1 cm/y) terranes is best dated by U–Pb analysis of coesite-bearing zircon domains coupled with Sm–Nd and Lu–Hf garnet analysis.><1 cm/y) terranes is best dated by U–Pb analysis of coesite-bearing zircon domains coupled with Sm–Nd and Lu–Hf garnet analysis.

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Constructing the Pressure–Temperature Path of Ultrahigh-Pressure Rocks

Coesite and diamond in metamorphic rocks point to their very deep burial, but these minerals do not allow a precise derivation of metamorphic pressure–temperature (P–T) conditions at ultrahigh pressure (UHP). Thermodynamic calculations of mineral equilibria can accomplish this task when it is possible to assign mineral compositions to a former UHP equilibrium state. Pressure–temperature pseudosections are superior, because they often permit the construction of P–T paths to and from UHP conditions only on the basis of chemically zoned minerals such as garnet and phengite. The examples of a metapelite from Oman and an eclogite from the Erzgebirge, Germany, illustrate this method, but also demonstrate its limits. The derived paths are the basis for further geodynamic modeling and insight into tectonic processes.

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Continental Crust at Mantle Depths: Key Minerals and Microstructures

Finding evidence for ultrahigh-pressure (UHP) metamorphism in crustal rocks is far from straightforward. The index minerals coesite and diamond are incredibly inconspicuous and are therefore difficult to use as UHP prospecting tools. Consequently, petrographers rely on recognizing subtle breakdown microstructures that result from pressure release during the return to the surface of the once deeply buried rock. Similarly, many other UHP minerals are first suspected on the basis of typical reaction or exsolution microstructures. Thus, the painstaking use of microscopic techniques has been fundamental to the tremendous advances in characterizing, quantifying, and understanding macroscopic-scale, deep continental subduction, rapid exhumation, and mountain-building processes.

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The Realm of Ultrahigh Pressure Metamorphism

The discovery of diamond and coesite in crustal rocks is compelling evidence that continental material has experienced pressures that can only be achieved at mantle depths. At least 20 terranes of unequivocal continental crust containing diamond or coesite are now recognized around the globe; their study constitutes a new field in petrology called ultrahigh-pressure metamorphism. The idea that continents do not subduct has given way to the notion that Earth has been sufficiently cool since the Cryogenian (~850 Ma) to allow density changes to drive continental crust into the mantle during collision. Some of this crust is exhumed to the surface, some pools at the Moho, and the rest sinks into the mantle. In this issue, microscopic observations, phase-equilibrium modeling, geochronology, and geodynamic modeling track the journey of crustal rocks to the mantle and back to Earth’s surface.

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