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1. Uranium Redox and Deposition Transitions Embedded in Deep‐Time Geochemical Models and Mineral Chemistry Networks

   https://doi.org/10.1029/2023GC011267  

   Moore, E_K; Li, J.; Zhang, A.; Hao, J.; Morrison, S_M; Hummer, D_R; Yee, N. (February 2024, Geochemistry, Geophysics, Geosystems)

   Abstract Uranium (U) is an important global energy resource and a redox sensitive trace element that reflects changing environmental conditions and geochemical cycling. The redox evolution of U mineral chemistry can be interrogated to understand the formation and distribution of U deposits and the redox processes involved in U geochemistry throughout Earth history. In this study, geochemical modeling using thermodynamic data, and mineral chemistry network analysis are used to investigate U geochemistry and deposition through time. The number of U⁶⁺mineral localities surpasses the number of U⁴⁺mineral localities in the Paleoproterozoic. Moreover, the number of sedimentary U⁶⁺mineral localities increases earlier in the Phanerozoic than the number of U⁴⁺sedimentary mineral localities, likely due to the necessity of sufficient sedimentary organic matter to reduce U⁶⁺–U⁴⁺. Indeed, modeling calculations indicate that increased oxidative weathering due to surface oxygenation limited U⁴⁺uraninite (UO₂) formation from weathered granite and basalt. Louvain network community detection shows that U⁶⁺forms minerals with many more shared elements and redox states than U⁴⁺. The range of weighted Mineral Element Electronegativity Coefficient of Variation (wMEE_CV) values of U⁶⁺minerals increases through time, particularly during the Phanerozoic. Conversely, the range of wMEE_CVvalues of U⁴⁺minerals is consistent through time due to the relative abundance of uraninite, coffinite, and brannerite. The late oxidation and formation of U⁶⁺minerals compared to S⁶⁺minerals illustrates the importance of the development of land plants, organic matter deposition, and redox‐controlled U deposition from ground water in continental sediments during this time‐period. 

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2. Bistability in the redox chemistry of sediments and oceans

   https://doi.org/10.1073/pnas.2008235117  

   van de Velde, Sebastiaan J.; Reinhard, Christopher T.; Ridgwell, Andy; Meysman, Filip J. (December 2020, Proceedings of the National Academy of Sciences)

   null (Ed.)

   For most of Earth’s history, the ocean’s interior was pervasively anoxic and showed occasional shifts in ocean redox chemistry between iron-buffered and sulfide-buffered states. These redox transitions are most often explained by large changes in external inputs, such as a strongly altered delivery of iron and sulfate to the ocean, or major shifts in marine productivity. Here, we propose that redox shifts can also arise from small perturbations that are amplified by nonlinear positive feedbacks within the internal iron and sulfur cycling of the ocean. Combining observational evidence with biogeochemical modeling, we show that both sedimentary and aquatic systems display intrinsic iron–sulfur bistability, which is tightly linked to the formation of reduced iron–sulfide minerals. The possibility of tipping points in the redox state of sediments and oceans, which allow large and nonreversible geochemical shifts to arise from relatively small changes in organic carbon input, has important implications for the interpretation of the geological rock record and the causes and consequences of major evolutionary transitions in the history of Earth’s biosphere. 

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3. Detecting upland glaciation in Earth’s pre-Pleistocene record

   https://doi.org/10.3389/feart.2022.904787  

   Soreghan, Gerilyn S.; Pfeifer, Lily S.; Sweet, Dustin E.; Heavens, Nicholas G. (August 2022, Frontiers in Earth Science)

   Earth has sustained continental glaciation several times in its past. Because continental glaciers ground to low elevations, sedimentary records of ice contact can be preserved from regions that were below base level, or subject to subsidence. In such regions, glaciated pavements, ice-contact deposits such as glacial till with striated clasts, and glaciolacustrine or glaciomarine strata with dropstones reveal clear signs of former glaciation. But assessing upland (mountain) glaciation poses particular challenges because elevated regions typically erode, and thus have extraordinarily poor preservation potential. Here we propose approaches for detecting the former presence of glaciation in the absence or near-absence of ice-contact indicators; we apply this specifically to the problem of detecting upland glaciation, and consider the implications for Earth’s climate system. Where even piedmont regions are eroded, pro- and periglacial phenomena will constitute the primary record of upland glaciation. Striations on large (pebble and larger) clasts survive only a few km of fluvial transport, but microtextures developed on quartz sand survive longer distances of transport, and record high-stress fractures consistent with glaciation. Proglacial fluvial systems can be difficult to distinguish from non-glacial systems, but a preponderance of facies signaling abundant water and sediment, such as hyperconcentrated flood flows, non-cohesive fine-grained debris flows, and/or large-scale and coarse-grained cross-stratification are consistent with proglacial conditions, especially in combination with evidence for cold temperatures, such as rip-up clasts composed of noncohesive sediment, indicating frozen conditions, and/or evidence for a predominance of physical over chemical weathering. Other indicators of freezing (periglacial) conditions include frozen-ground phenomena such as fossil ice wedges and ice crystals. Voluminous loess deposits and eolian-marine silt/mudstone characterized by silt modes, a significant proportion of primary silicate minerals, and a provenance from non-silt precursors can indicate the operation of glacial grinding, even though such deposits may be far removed from the site(s) of glaciation. Ultimately, in the absence of unambiguous ice-contact indicators, inferences of glaciation must be grounded on an array of observations that together record abundant meltwater, temperatures capable of sustaining glaciation, and glacial weathering (e.g., glacial grinding). If such arguments are viable, they can bolster the accuracy of past climate models, and guide climate modelers in assessing the types of forcings that could enable glaciation at elevation, as well as the extent to which (extensive) upland glaciation might have influenced global climate. 

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4. Subaerial oxidative uranium mobilization at the culmination of the Great Oxidation Event

   https://doi.org/10.1073/pnas.2510289122  

   Bauer, Ann M; Li, Weiqiang; Rybacki, Kyle S; Roden, Eric E; Kump, Lee R; Johnson, Clark M (September 2025, Proceedings of the National Academy of Sciences)

   Redox-sensitive elements figure prominently in studies of the evolution of Earth’s surface redox state, including the first major rise in atmospheric O₂, the Paleoproterozoic Great Oxidation Event. Most Precambrian rocks endured multistage tectonothermal histories, however, adding ambiguity to interpretation of their chemistry. Here, we apply U-Th-Pb isotope geochronology to the highly oxidized ~2.06 Ga Kuetsjärvi Volcanic Formation, Pechenga Greenstone Belt, Russia, to constrain the age and extent of U oxidation. By contrasting the relative mobility of U and Th using Pb isotopes, we find that complete to near-complete oxidation and removal of U occurred shortly after eruption. We argue that this likely indicates relatively high atmospheric O₂, where oxidative weathering and alteration produced a global pulse of U to the oceans. Such a pulse could explain widespread shifts in the U-Th-Pb isotope character of mantle reservoirs at ~2 Ga, including a decrease in the²³²Th/²³⁸U ratio of the mid-ocean ridge basalt source and inception of the high-²³⁸U/²⁰⁴Pb (HIMU) source to ocean island basalts, underscoring the connections between the redox character of the Paleoproterozoic surface and deep Earth. Using²⁰⁷Pb-²⁰⁶Pb,²³⁸U-²⁰⁶Pb,²³⁵U-²⁰⁷Pb, and²³²Th-²⁰⁸Pb geochronology, ~2.06 Ga oxidative loss of U may be distinguished from reintroduction of U at ~1.8 Ga during regional metamorphism, as well as Pb loss during a Phanerozoic tectonothermal event. Our results therefore establish the complex history of redox-sensitive element behavior in the rocks, highlighting the fact that elemental abundances, by themselves, are unlikely to capture straightforward proxy information in rocks that have seen multistage geologic histories. 

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5. Reversal of carbonate-silicate cation exchange in cold slabs in Earth’s lower mantle

   https://doi.org/10.1038/s41467-021-21761-9  

   Lv, Mingda; Dorfman, Susannah M.; Badro, James; Borensztajn, Stephan; Greenberg, Eran; Prakapenka, Vitali B. (December 2021, Nature Communications)

   Abstract The stable forms of carbon in Earth’s deep interior control storage and fluxes of carbon through the planet over geologic time, impacting the surface climate as well as carrying records of geologic processes in the form of diamond inclusions. However, current estimates of the distribution of carbon in Earth’s mantle are uncertain, due in part to limited understanding of the fate of carbonates through subduction, the main mechanism that transports carbon from Earth’s surface to its interior. Oxidized carbon carried by subduction has been found to reside in MgCO 3 throughout much of the mantle. Experiments in this study demonstrate that at deep mantle conditions MgCO 3 reacts with silicates to form CaCO 3 . In combination with previous work indicating that CaCO 3 is more stable than MgCO 3 under reducing conditions of Earth’s lowermost mantle, these observations allow us to predict that the signature of surface carbon reaching Earth’s lowermost mantle may include CaCO 3 . 

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