Thematic Articles

Redox Processes in Early Earth Accretion and in Terrestrial Bodies

The Earth is a unique rocky planet with liquid water at the surface and an oxygen-rich atmosphere, consequences of its particular accretion history. The earliest accreting bodies were small and could be either differentiated and undifferentiated; later larger bodies had formed cores and mantles with distinct properties. In addition, there may have been an overall trend of early reduced and later oxidized material accreting to form the Earth. This paper provides an overview—based on natural materials in our Earthbound sample collections, experimental studies on those samples, and calculations and numerical simulations of differentiation processes—of planetary accretion, core–mantle equilibration, mantle redox processes, and redox variations in Earth, Mars, and other terrestrial bodies.

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The Redox Boundaries of Earth’s Interior

The interior of the Earth is an important reservoir for elements that are chemically bound in minerals, melts, and gases. Analyses of the proportions of redox-sensitive elements in ancient and contemporary natural rocks provide information on the temporal redox evolution of our planet. Natural inclusions trapped in diamonds, xenoliths, and erupted magmas provide unique windows into the redox conditions of the deep Earth, and reveal evidence for heterogeneities in the mantle’s oxidation state. By examining the natural rock record, we assess how redox boundaries in the deep Earth have controlled elemental cycling and what effects these boundaries have had on the temporal and chemical evolution of oxygen fugacity in the Earth’s interior and atmosphere.

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Earth’s Electrodes

The oxidation–reduction (‘redox’) state is an important intensive property of any geologic system and is typically measured (and reported) as either the redox potential (Eh) or the oxygen fugacity (fO2). These two concepts cover the whole spectrum of geologic systems: from low-temperature aqueous and sedimentary systems to high-temperature rock-forming environments. The redox state determines the speciation of a fluid phase and exercises fundamental controls on phase relations and geochemical evolution. Here, we review the concepts that underpin the redox state and outline a framework for describing and quantifying the concept of the oxidation state.

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From Mine to Mind and Mobiles: Society’s Increasing Dependence on Lithium

Lithium is everywhere. If you have a mobile phone or a laptop, you are taking advantage of one of the technological revolutions of the last 30 years: lithium-ion batteries. Lithium has long been used in pharmaceuticals and in the manufacture of grease, ceramics, and glass, but has now become the symbolic element of the current energy revolution. Lithium is ubiquitous in our society and plays a role in our lives that could not have been previously imagined. From its mining to its applications in advanced battery materials and pharmaceuticals, welcome to the lithium decade. Electric mobility will become the new normal.

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Classification and Characteristics of Natural Lithium Resources

There are three broad types of economic lithium deposit: 1) peralkaline and peraluminous pegmatite deposits and their associated metasomatic rocks; 2) Li-rich hectorite clays derived from volcanic deposits; 3) salar evaporites and geothermal deposits. Spodumene-bearing pegmatites are the most important and easily exploitable Li deposits, typically containing 0.5 Mt Li. Salar deposits hold the largest Li reserves, can reach up to 7 Mt Li, but are more difficult to exploit. Allowing for recycling, the current predicted demand up to the year 2100 is 20 Mt Li; world resources are currently estimated at more than 62 Mt Li. Thus, abundant resources exist, and no long-term shortage is predicted.

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Lithium and Lithium Isotopes in Earth’s Surface Cycles

Lithium and its isotopes can provide information on continental silicate weathering, which is the primary natural drawdown process of atmospheric CO2 and a major control on climate. Lithium isotopes themselves can help our understanding of weathering, via globally important processes such as clay formation and cation retention. Both these processes occur as part of weathering in modern surface environments, such as rivers, soil pore waters, and groundwaters, but Li isotopes can also be used to track weathering changes across major climate-change events. Lithium isotope evidence from several past climatic warming and cooling episodes shows that weathering processes respond rapidly to changes in temperature, meaning that weathering is capable of bringing climate back under control within a few tens of thousands of years.

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High-Temperature Processes: Is it Time for Lithium Isotopes?

The field of high-temperature Li isotope geochemistry has been rattled by major paradigm changes. The idea that Li isotopes could be used to trace the sources of fluids, rocks, and magmas had to be largely abandoned, because Li diffusion causes its isotopes to fractionate at metamorphic and magmatic temperatures. However, diffusive fractionation of Li isotopes can be used to determine timescales of geologic processes using arrested diffusion profiles. High diffusivity and strong kinetic isotope fractionation favors Li isotopes as a tool to constrain the durations of fast processes in the crust and mantle, where other geochronometers fall short. Time may be the parameter that high-temperature Li isotope studies will be able to shed much light on.

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The Cosmic Lithium Story

Lithium’s story spans the history of the universe and is one that links to all its largest-scale processes: big bang nucleosyntheses, the evolution of stars, and galactic chemical evolution. Lithium was the only metal produced in the big bang, alongside the gases H and He. Stars destroy both stable isotopes of Li easily, yet we still have Li today, even after generations of stars have come and gone. Ongoing production of Li by galactic cosmic rays and by a limited number of Li-producing nuclear reactions and transport processes in some rare types of stars keeps lithium present in the universe.

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The Minerals of Lithium

Lithium is rare in the cosmos, but the formation of continental crust has concentrated lithium into economic deposits. The 124 recognized Li mineral species occur largely in four geologic environments: (1) lithium–cesium–tantalum (LCT) granitic pegmatites and associated metasomatic rocks; (2) highly peralkaline pegmatites; (3) metasomatic rocks not directly associated with pegmatites; (4) manganese deposits. The geologically oldest Li minerals are reported from LCT pegmatites and date to 3,000–3,100 Ma, a critical period in the evolution of the continental crust and the rate of its generation. This suggests a link between the earliest appearance of LCT-family pegmatites and the onset of plate tectonics, consistent with the correlation between the observed abundance of LCT-family pegmatites and supercontinent assembly.

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Lazed and Diffused: Untangling Noble Gas Thermochronometry Data for Exhumation Rates

Thermochronometric data can record the thermal history of rocks as they cool from high temperatures at depth to lower temperatures at the surface. This provides a unique perspective on the tectonic processes that form topography and the erosional processes that destroy it. However, quantitatively interpreting such data is a challenge because multiple models can do an equally good job at reproducing the data. In this article, we describe how inverse modeling can be used to improve quantitative interpretations of noble gas thermochronometric data on a variety of scales, ranging from mountain belts to individual mineral grains.

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