Thematic Articles

Luminescence Applications in Petrology

Luminescence is a powerful tool to infer physical and chemical conditions during mineral growth. It is very subtly linked to temperature of formation, composition and structural state, and related changes during rock evolution that often cause striking contrasts in the light emitted. This information can show magma sources and the hydrothermal evolution of igneous rocks, sources and diagenesis in sedimentary systems, and the pressure–temperature evolution during metamorphism. However, luminescence is most powerful when it goes beyond imaging, coupling with spectroscopies and microgeochemical techniques. We present examples of luminescence spectroscopies in igneous, sedimentary, and metamorphic rocks to show how these methods elucidate geological processes. Luminescence imaging is an exciting scientific frontier in which novel methods provide ever deeper insights into petrogenesis.

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Luminescence Images: What is it That You See?

Luminescence imaging and hyperspectral luminescence mapping are powerful analytical tools with widespread applications in geosciences and materials science. The luminescence of minerals is mainly a defect phenomenon caused by lattice defects and/or impurity elements. This in turn allows one to study trace-element composition and the structural state of a sample by means of its emission. One of the most spectacular and widely used applications of luminescence images is to visualise internal textures in minerals that are not revealed by other analytical techniques. Herein we present a selection of examples for the extraordinary sensitivity of luminescence imaging. We also show that precise information on samples is obtained if luminescence imaging is combined with spectroscopic analysis of the emission and/ or complementary analytical techniques.

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Activators in Minerals and the Role of Electronic Defects

Luminescence in minerals is created by ions, groups of ions, or electronic defects that can absorb energy and emit it as visible light. These units are commonly referred to as “centers” or “activators.” They can be impurities in the mineral or intrinsic constituents. In some cases, separate ions (so-called “sensitizers”) act to aid the luminescence process by preferentially absorbing energy and sending it to the emitting unit. In other cases, ions or electronic defects can slow the emission process by trapping excited electrons. Ions preventing emission from other luminescence centers are called “quenchers.” Some impurities can potentially create almost any luminescent color, while others are known for particular colored emission. Luminescence may exhibit strong zonation in crystals due to selective uptake of the activating ions.

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Luminescence: The “Cold Glow” of Minerals

Luminescence is the eye-catching phenomenon of light emission by a mineral after some input of energy (the excitation). Although commonly used in Earth sciences only to produce images, much more can be extracted from this phenomenon. Luminescence is extremely sensitive to low levels of emitters (activators), which helps to reveal the geochemistry or the creation of defects. We give an overview of the great variety of techniques (cathodoluminescence, photoluminescence, and more), discuss vocabulary issues (such as excitation versus stimulation, or the different types of persistent luminescence phenomena), and propose wording we feel best reflects today’s knowledge. We explain the basics of luminescence spectroscopy with emission, excitation, and time-resolved spectra to obtain useful data for Earth scientists.

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The Geological History of Water: From Earth’s Accretion to the Modern Deep Water Cycle

The abundance of water on Earth and its distribution between surficial and deep reservoirs are the outcome of 4.6 billion years of geological history involving various mechanisms of water in and outgassing. Here, we use the metaphor of a pipeline connecting Earth’s deep and surface water reservoirs. The net flux through this pipeline has changed over time due to contrasting Hadean, Archean, and modern geodynamic regimes. Most water was dissolved in the primordial magma ocean, entrapped in the solidifying mantle, and massively released by volcanism during the Hadean and Archaean. As Earth cooled, plate tectonics enabled water ingassing into the mantle, which appears to exceed outgassing under the modern tectonic regime, implying that Earth’s surface has been drying out and will continue to do so.

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Probing Deep Hydrogen Using Electrical Conductivity

Electrical conductivity is perhaps the physical property of rocks that is most sensitive to the presence of hydrogen. Hydrogen enhances conductivity via proton conduction in minerals or by stabilizing highly conductive phases, such as hydrous silicate melts or aqueous fluids. Hydrogen might also be stored in the metallic core. Electrical conductivity measurements in the laboratory can be used to interpret magnetotelluric maps of the mantle in terms of hydrogen content and distribution. In active tectonic settings like subduction zones, anomalously high conductivities have revealed the distribution and migration pathways of H-bearing melts and fluids, illuminating the transport of hydrogen in our planet’s interior.

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Hydrous Melting and its Seismic Signature

Hydrogen is known to affect elastic and anelastic properties of mantle rocks and minerals. Hydrogen dissolution in minerals notably alters the properties of transition zone phases, which may accommodate very high water contents. Moreover, even small amounts of water can induce partial melting in certain mantle regions and modify seismic wave velocities and attenuation. Progress in seismic imaging of the mantle—particularly the mapping of seismic attenuation and velocities—has improved constraints on local hydrous melt content in the upper mantle, and evidence exists for partial melt–bearing layers above and below the transition zone owing to dehydration reactions induced by upward or downward flow of mantle material. Further observational and modeling studies are needed to more fully understand the influence of hydrous melting on the global water cycle, mantle viscosity, and large-scale geodynamics.

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Deep Hydrogen Reservoirs and Longevity

The oceans are voluminous H2O reservoirs that regulate climate and life on Earth. Yet much larger H2O reservoirs, potentially accounting for several oceans, may exist in the Earth’s mantle and core in the form of H atoms trapped into the structure of nominally anhydrous minerals (NAMs). H atoms trapped into the structure of nominally anhydrous minerals (NAMs) and metallic alloys. Determining the size of these ‘hidden oceans’ is key to understanding planetary evolution and surface dynamics and can be done by combining data from rare natural samples with experimental and theoretical models. The longevity of these deep H reservoirs is controlled by H transport rates over geological times, which are dominated by percolation rates, once H partitions into melts, or by plate mobility, if H remains locked in NAMs.

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The Subduction of Hydrogen: Deep Water Cycling, Induced Seismicity, and Plate Tectonics

The dynamic equilibrium between mantle degassing and water recycling in subduction zones controls the variation of sea level in deep geologic time, as well as the size of Earth’s interior hydrogen reservoir. While the principles of water transport and water release by common hydrous minerals in the subducted crust are relatively well understood, the importance of deep serpentinization of the slab, the contribution of nominally anhydrous minerals and dense hydrous magnesium silicates to water transport, and the mechanisms of water subduction into the lower mantle are still subjects of active research. A quantitative understanding of these processes is required to constrain the evolution of Earth’s deep water cycle through geologic time and the role of water in stabilizing plate tectonics.

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Hydrogen in the Deep Earth

Hydrogen is one of the most difficult elements to characterize in geological materials. Even at trace levels, hydrogen has a major impact on the properties of minerals, silicate melts, and fluids, and thus on the physical state of the mantle and crust. The investigation of H-bearing species in deep minerals, melts, and fluids is challenging because these phases can be strongly modified during transport to Earth’s surface. Furthermore, interpretation of experimental studies can be clouded by kinetic inhibitions and other artifacts. Nevertheless, recent improvements in analytical, experimental, and modeling methodologies have enabled advances in our understanding of how hydrogen is incorporated in the deep Earth, which is essential for constraining hydrogen cycling and storage through geologic time.

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