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1. Uranium Isotope Fractionation in Non‐sulfidic Anoxic Settings and the Global Uranium Isotope Mass Balance

   https://doi.org/10.1029/2020GB006649  

   Cole, Devon B.; Planavsky, Noah J.; Longley, Martha; Böning, Philipp; Wilkes, Daniel; Wang, Xiangli; Swanner, Elizabeth D.; Wittkop, Chad; Loydell, David K.; Busigny, Vincent; et al (August 2020, Global Biogeochemical Cycles)

   Abstract Uranium isotopes (²³⁸U/²³⁵U) have been used widely over the last decade as a global proxy for marine redox conditions. The largest isotopic fractionations in the system occur during U reduction, removal, and burial. Applying this basic framework, global U isotope mass balance models have been used to predict the extent of ocean floor anoxia during key intervals throughout Earth's history. However, there are currently minimal constraints on the isotopic fractionation that occurs during reduction and burial in anoxic and iron‐rich (ferruginous) aquatic systems, despite the consensus that ferruginous conditions are thought to have been widespread through the majority of our planet's history. Here we provide the first exploration of δ²³⁸U values in natural ferruginous settings. We measured δ²³⁸U in sediments from two modern ferruginous lakes (Brownie Lake and Lake Pavin), the water column of Brownie Lake, and sedimentary rocks from the Silurian‐Devonian boundary that were deposited under ferruginous conditions. Additionally, we provide new δ²³⁸U data from core top sediments from anoxic but nonsulfidic settings in the Peru Margin oxygen minimum zone. We find that δ²³⁸U values from sediments deposited in all of these localities are highly variable but on average are indistinguishable from adjacent oxic sediments. This forces a reevaluation of the global U isotope mass balance and how U isotope values are used to reconstruct the evolution of the marine redox landscape. 

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2. Geochemical data from sediments and porewaters from ferruginous and meromictic Brownie Lake, Minnesota, U.S.A.

   https://doi.org/10.6073/pasta/68b50baa0a767ab33f2b7dd91948036e  

   Swanner, Elizabeth D.; Islam, Raisa; Ledesma, Gabrielle; Wittkop, Chad; Akam, Sajjad; Eitel, Eryn; Katsev, Sergei; Johnson, Ben; Poulton, Simon; Bray, Andy (January 2022, Environmental Data Initiative)

   The dataset is comprised of analyses of sediment cores and sediment trap samples from ferruginous and meromictic Brownie Lake, Minnesota, U.S.A from January 2018 through February 2021. The dataset includes bulk sediment characteristics including water content, grain size, major and minor elements. Voltammetric scans were collected on porewaters and lake waters. Sediment porewaters were analyzed for pH, total alkalinity, ferrous iron, and dissolved sulfur species contents. Sediment samples were maintained under the exclusion of oxygen for analysis by synchrotron-based X-ray absorption spectroscopy. 

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3. Iron cycling and isotopic fractionation in a ferruginous, seasonally ice-covered lake

   https://doi.org/10.1016/j.gca.2024.07.037  

   Heard, Andy W; Ostrander, Chadlin M; Swanner, Elizabeth D; Rico, Kathryn; Nielsen, Sune G (October 2024, Geochimica et Cosmochimica Acta)

   Ferruginous conditions, defined by anoxia and abundant dissolved ferrous iron (Fe2+aq), dominated the Precambrian oceans but are essentially non-existent in a modern, oxygenated world. Ferruginous meromictic lakes represent natural laboratories to ground truth our understanding of the stable Fe isotope proxy, which has been used extensively in interpreting the origins of Fe-rich sedimentary rocks like iron formations (IFs) and the interactions of early life with high-Fe2+aq conditions. Here we report comprehensive geochemical and Fe isotopic analyses of samples collected in May and August 2022, and March 2023, from Deming Lake, Minnesota, a ferruginous meromictic lake that undergoes surface freezing in winter and never becomes euxinic. Through chemical and Fe isotopic analyses of different putative Fe sources to Deming Lake; including eolian input trapped in winter ice cover, nearby bogs, and regional groundwaters sampled at surface springs; we find that a groundwater source provides the best chemical and Fe isotopic match for Deming Lake and can support Fe2+aq-rich waters at depth that maintain a permanent chemocline at ~12 m. The ice-free Deming Lake water column can be split into three layers dominated by distinct Fe cycling regimes. Layer (I) extends from the lake surface to the base of the oxycline at ~6 m, and its Fe cycling is dominated by isotopically light Fe uptake into biomass, likely from stabilized dissolved Fe3+, with variable eolian lithogenic influences. Layer (II) extends between the oxycline and the chemocline at ~12 m and is dominated by partial Fe2+aq oxidation on approach to the oxycline, with the formation of variably isotopically heavy Fe3+-bearing particles. Layer (III) underlies the chemocline and is defined by Fe2+ phosphate (vivianite) and carbonate saturation and precipitation under anoxic, Fe2+aq-rich conditions with little Fe isotopic fractionation. The ice-covered winter water column features more homogenous Fe chemistry above the chemocline, which we attribute to seasonal homogenization of Layers (I) and (II), with suppressed ferric particle formation. Authigenic Fe minerals with non-crustal (light) Fe isotopic compositions only appreciably accumulate in sediments in Deming Lake underlying the chemocline. All sediments deposited above 12 m appear crustal in their Fe isotopic, Mn/Fe, and Fe/Al ratios, likely revealing efficient reductive dissolution of Fe3+-bearing lake precipitates and remineralization of Fe-bearing biomass. We find limited fractionation of Fe isotopes in the ice-covered water column and suggest this provides evidence that substantial delivery of oxidants is required to generate highly fractionated Fe isotopic compositions in Sturtian Snowball era IFs. By comparing Fe isotopic and Mn/Fe fractionation trends in the different Deming Lake layers, we also suggest that correlations between these two parameters in giant early Paleoproterozoic IFs requires the simultaneous deposition of multiple authigenic phases on the ancient seafloor. Finally, high-precision triple Fe isotopic analyses of dissolved Fe impacted by extensive oxidation near the Deming Lake oxycline reveal that the slope of the mass fractionation law for natural, O2-mediated Fe2+aq oxidation is identical to those previously defined for both UV photo-oxidation, and for an array of highly fractionated Paleoproterozoic IFs. 

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4. Prediction of organic geochemical parameters from inorganic geochemical data in the Cretaceous-Danian Moreno Formation, San Joaquin Basin, California

   https://doi.org/10.1016/j.chemgeo.2024.122551  

   Olson, Hunter C; Scheirer, Allegra Hosford; Ritzer, Samantha R; Sperling, Erik A (February 2025, Chemical Geology)

   Accurately reconstructing original Total Organic Carbon (TOC) in thermally mature rocks is essential for the correct application of geochemical proxies and understanding organic carbon burial through time. To reconstruct original TOC using empirical methods, it is vital to have an accurate estimate of the original Hydrogen Index (HI). The two most common methods are estimating original HI using kerogen type or using average HI values from immature rocks elsewhere in the basin. This study tests the ability to use inorganic geochemical data to reconstruct original HI using the Upper Cretaceous-Paleogene Moreno Formation from the San Joaquin Basin, California, USA as a case study. The study utilized cores from the Moreno Formation that are thermally immature, thus preserving original HI values, and that span a range in initial HI. First, inorganic geochemical data were produced (elemental abundances and iron speciation) for samples previously analyzed for organic geochemistry. These data suggest that bottom water conditions during deposition of the Moreno Formation were ferruginous (anoxic and non-sulfidic), without development of sustained euxinia (anoxic and sulfidic). Next, a random forest machine learning analysis was implemented to analyze which inorganic geochemical variables best predict HI in the Moreno Formation. The most important proxies were those for detrital input (Ti, Th), marine export productivity (Cu, Ni), and redox proxies for suboxic conditions (Se, Cr, iron speciation). Finally, the random forest framework was used to predict HI values for three main study cores based on their inorganic geochemistry. These predictions were compared stratigraphically and statistically against the measured values and the kerogen type and average HI methods for reconstructing HI and show this new method has better predictive power than approaches based on single values. This indicates strong promise for using inorganic geochemistry, which is relatively immune to thermal maturation, to reconstruct organic geochemical parameters that are modified during burial and diagenetic process. 

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5. Decadal-scale hotspot methane ebullition within lakes following abrupt permafrost thaw

   https://doi.org/10.1088/1748-9326/abc848  

   Walter Anthony, K. M.; Lindgren, P.; Hanke, P.; Engram, M.; Anthony, P.; Daanen, R. P.; Bondurant, A.; Liljedahl, A. K.; Lenz, J.; Grosse, G.; et al (February 2021, Environmental Research Letters)

   Abstract Thermokarst lakes accelerate deep permafrost thaw and the mobilization of previously frozen soil organic carbon. This leads to microbial decomposition and large releases of carbon dioxide (CO₂) and methane (CH₄) that enhance climate warming. However, the time scale of permafrost-carbon emissions following thaw is not well known but is important for understanding how abrupt permafrost thaw impacts climate feedback. We combined field measurements and radiocarbon dating of CH₄ebullition with (a) an assessment of lake area changes delineated from high-resolution (1–2.5 m) optical imagery and (b) geophysical measurements of thaw bulbs (taliks) to determine the spatiotemporal dynamics of hotspot-seep CH₄ebullition in interior Alaska thermokarst lakes. Hotspot seeps are characterized as point-sources of high ebullition that release¹⁴C-depleted CH₄from deep (up to tens of meters) within lake thaw bulbs year-round. Thermokarst lakes, initiated by a variety of factors, doubled in number and increased 37.5% in area from 1949 to 2009 as climate warmed. Approximately 80% of contemporary CH₄hotspot seeps were associated with this recent thermokarst activity, occurring where 60 years of abrupt thaw took place as a result of new and expanded lake areas. Hotspot occurrence diminished with distance from thermokarst lake margins. We attribute older¹⁴C ages of CH₄released from hotspot seeps in older, expanding thermokarst lakes (¹⁴C_CH420 079 ± 1227 years BP, mean ± standard error (s.e.m.) years) to deeper taliks (thaw bulbs) compared to younger¹⁴C_CH4in new lakes (¹⁴C_CH48526 ± 741 years BP) with shallower taliks. We find that smaller, non-hotspot ebullition seeps have younger¹⁴C ages (expanding lakes 7473 ± 1762 years; new lakes 4742 ± 803 years) and that their emissions span a larger historic range. These observations provide a first-order constraint on the magnitude and decadal-scale duration of CH₄-hotspot seep emissions following formation of thermokarst lakes as climate warms. 

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