Thematic Articles

The Behavior of H2 in Aqueous Fluids under High Temperature and Pressure

The presence of H2 and H2O in planetary interiors prompts the need for fundamental studies on these compounds under corresponding conditions. Here, we summarize data on H2 properties in aqueous systems under conditions of high temperature and pressure. We explain how to measure important H2 fugacities in hydrothermal systems. We present available experimental data and thermodynamic models for H2 solubility and vapor–liquid partitioning under hydrothermal conditions. In addition, we introduce the fascinating world of H2–H2O clathrate hydrates under extreme temperatures and pressures. The properties of the H2–H2O system are well established below the critical point of water (374 °C and 22.06 MPa), but far less is known under higher temperatures and pressures, or the effect of salt.

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Abiotic Synthesis of Methane and Organic Compounds in Earth’s Lithosphere

Accumulation of molecular hydrogen in geologic systems can create conditions energetically favorable to transform inorganic carbon into methane and other organic compounds. Although hydrocarbons with a potentially abiotic origin have been proposed to form in a number of crustal settings, the ubiquitous presence of organic compounds derived from biological organic matter presents a challenge for unambiguously identifying abiotic organic molecules. In recent years, extensive analysis of methane and other organics in diverse geologic fluids, combined with novel isotope analyses and laboratory simulations, have, however, yielded insights into the distribution of specific abiotic organic molecules in Earth’s lithosphere and the likely conditions and pathways under which they form.

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Abiotic Sources of Molecular Hydrogen on Earth

The capacity for molecular hydrogen (H2) to hydrogenate oxygen and carbon is critical to the origin of life and represents the basis for all known life-forms. Major sources of H2 that strictly involve nonbiological processes and inorganic reactants include (1) the reduction of water during the oxidation of iron in minerals, (2) water splitting due to radioactive decay, (3) degassing of magma at low pressures, and (4) the reaction of water with surface radicals during mechanical breaking of silicate rocks. None of these processes seem to significantly affect the current global atmospheric budget of H2, yet there is substantial H2 cycling in a wide range of Earth’s subsurface environments, with multifaceted implications for microbial ecosystems.

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Hydrogen and Abiotic Hydrocarbons: Molecules that Change the World

Molecular hydrogen (H2), methane, and hydrocarbons with an apparent abiotic origin have been observed in a variety of geologic settings, including serpentinized ultramafic rocks, hydrothermal fluids, and deep fractures within ancient cratons. Molecular hydrogen is also observed in vapor plumes emanating from the icy crust of Saturn’s moon Enceladus, and methane has been detected in the atmosphere of Mars. Geologic production of these compounds has been the subject of increasing scientific attention due to their use by chemosynthetic biological communities. These compounds are also of interest as possible energy resources. This issue summarizes the geological sources of abiotic H2 and hydrocarbons on Earth and elsewhere and examines their impact on microbial life and energy resources.

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New Trends in Raman Spectroscopy: From High-Resolution Geochemistry to Planetary Exploration

This article reviews nonconventional Raman spectroscopy techniques and discusses present and future applications of these techniques in the Earth and planetary sciences. Time-resolved spectroscopy opens new ways to limit or exploit luminescence effects, whereas techniques based on coherent anti-Stokes Raman scattering (CARS) or surface-enhanced Raman spectroscopy (SERS) allow the Raman signal to be considerably enhanced even down to very high spatial resolutions. In addition, compact portable Raman spectrometers are now routinely used out of the laboratory and are even integrated to two rovers going to Mars in the near future.

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Geoscience Meets Biology: Raman Spectroscopy in Geobiology and Biomineralization

Raman spectroscopy is widely applied in metamorphic petrology and offers many opportunities for geological and tectonic research. Minimal sample preparation preserves sample integrity and microtextural information, while use with confocal microscopes allows spatial resolution down to the micrometer level. Raman spectroscopy clearly distinguishes mineral polymorphs, providing crucial constraints on metamorphic conditions, particularly ultrahigh-pressure conditions. Raman spectroscopy can also be used to monitor the structure of carbonaceous material in metamorphic rocks. Changes in structure are temperature-sensitive, so Raman spectroscopy of carbonaceous material is widely used for thermometry. Raman spectroscopy can also detect and quantify strain in micro-inclusions, offering new barometers that can be applied to understand metamorphic and tectonic processes without any assumptions about chemical equilibrium.

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Applications of Raman Spectroscopy in Metamorphic Petrology and Tectonics

Raman spectroscopy is widely applied in metamorphic petrology and offers many opportunities for geological and tectonic research. Minimal sample preparation preserves sample integrity and microtextural information, while use with confocal microscopes allows spatial resolution down to the micrometer level. Raman spectroscopy clearly distinguishes mineral polymorphs, providing crucial constraints on metamorphic conditions, particularly ultrahigh-pressure conditions. Raman spectroscopy can also be used to monitor the structure of carbonaceous material in metamorphic rocks. Changes in structure are temperature-sensitive, so Raman spectroscopy of carbonaceous material is widely used for thermometry. Raman spectroscopy can also detect and quantify strain in micro-inclusions, offering new barometers that can be applied to understand metamorphic and tectonic processes without any assumptions about chemical equilibrium.

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Applications of Raman Spectroscopy in Mineralogy and Geochemistry

The application of Raman spectroscopy for the identification and characterization of minerals and related materials has increased appreciably during recent years. Raman spectroscopy has proven to be a most valuable and versatile analytical tool. Successful applications cover virtually all the mineralogical sub-disciplines, and have become more numerous in geochemistry. We present a general summary of present applications, illustrated by selected examples. In addition, we briefly point out several aspects of spectral acquisition, data reduction, and interpretation of Raman results that are important for the application of Raman spectroscopy as a reliable analytical tool.

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Microscale Chemistry: Raman Analysis of Fluid and Melt Inclusions

Raman spectroscopy is a commonly applied nondestructive analytical technique for characterizing fluid and melt inclusions. The exceptional spatial resolution (~1 µm) and excellent spectral resolution (≤1 cm−1) permits the characterization of micrometer-scale phases and allows quantitative analyses based on Raman spectral features. Data provided by Raman analysis of fluid and melt inclusions has significantly advanced our understanding of complex geologic processes, including preeruptive volatile contents of magmas, the nature of fluids in the deep crust and upper mantle, the generation and evolution of methane-bearing fluids in unconventional hydrocarbon reservoirs. Anticipated future advances include the development of Raman mass spectroscopy and the use of Raman to monitor reaction progress in synthetic and natural fluid inclusion microreactors.

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Welcome to Raman Spectroscopy: Successes, Challenges, and Pitfalls

Geoscientists quickly recognized the broad applicability of Raman microprobe spectroscopy to the Earth and planetary sciences, especially after commercially built microprobe instruments became available in the early 1980s. Raman spectra are sensitive to even minor (chemical or structural) perturbations within chemical bonds in (even amorphous) solids, liquids, and gases and can, thus, help identify, characterize, and differentiate between individual minerals, fluid inclusions, glasses, carbonaceous materials, solid solution phases, strain in minerals, and dissolved species in multi-component solutions. The articles in this issue explore how Raman spectroscopy has deepened and broadened our understanding of geological and extraterrestrial materials and processes.

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