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1. 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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2. 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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3. Dissolved organic carbon dynamics are driven by water temperature, primary production, and anoxia over 5 years of whole-ecosystem experiments in a eutrophic reservoir

   https://doi.org/10.1007/s00027-025-01252-5  

   Hounshell, Alexandria G; Lewis, Abigail_S L; Howard, Dexter W; Wander, Heather L; Lofton, Mary E; Hanson, Paul C; Carey, Cayelan C (January 2026, Aquatic Sciences)

   Abstract Lakes and reservoirs play a key role in the global carbon cycle, representing important carbon sinks and sources within the terrestrial landscape under different environmental conditions. Changes in climate and land use have led to increased air and surface water temperatures; increased occurrence and duration of hypolimnetic anoxia; and altered hydrology and nutrient loading, which have the potential to affect how these freshwater ecosystems receive and process carbon. To assess how interacting environmental drivers influence carbon cycling in lakes and reservoirs, we used a 5-year whole-ecosystem experiment to investigate the effects of variable catchment, meteorology, and in-lake drivers on epilimnetic and hypolimnetic dissolved organic carbon in a small reservoir. Using a combination of whole-ecosystem models and time-series analyses, we found that primary production and other internal sources contributed a mean of 29% (range: 7–49%) of the dissolved organic carbon in the reservoir’s epilimnion over the 5-year period. We also found that sinking epilimnetic primary production, dissolved organic carbon from the sediments, and other factors were likely important sources of hypolimnetic dissolved organic carbon, especially during periods of anoxia. Both the epilimnion and hypolimnion were found to be intermittent sinks, yet net sources, of dissolved organic carbon. Overall, water temperature was identified as the most important environmental predictor for water-column dissolved organic carbon, with higher concentrations observed under seasonally elevated temperatures during the late summer and early fall. Our results suggest that lakes and reservoirs may become larger sources of dissolved organic carbon to downstream ecosystems in a warmer, more anoxic future. 

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4. Oxic methane production from methylphosphonate in a large oligotrophic lake: limitation by substrate and organic carbon supply

   https://doi.org/10.1128/aem.01097-23  

   Peoples, Logan M.; Dore, John E.; Bilbrey, Evan M.; Vick-Majors, Trista J.; Ranieri, John R.; Evans, Kate A.; Ross, Abigail M.; Devlin, Shawn P.; Church, Matthew J. (December 2023, Applied and Environmental Microbiology)

   Glass, Jennifer B. (Ed.)

   ABSTRACT While methane is typically produced under anoxic conditions, methane supersaturation in the presence of oxygen has been observed in both marine and fresh waters. The biological cleavage of methylphosphonate (MPn), which releases both phosphate and methane, is one pathway that may contribute to this paradox. Here, we explore the genomic and functional potential for oxic methane production (OMP) via MPn in Flathead Lake, a large oligotrophic freshwater lake in northwest Montana. Time series and depth profile measurements show that epilimnetic methane was persistently supersaturated despite high oxygen levels, suggesting a possiblein situoxic source. Metagenomic sequencing indicated that 10% of microorganisms in the lake, many of which are related to the Burkholderiales (Betaproteobacteria) and Actinomycetota, have the genomic capacity to cleave MPn. We experimentally demonstrated that these organisms produce methane stoichiometrically with MPn consumption across multiple years. However, methane was only produced at appreciable rates in the presence of MPn when a labile organic carbon source was added, suggesting that this process may be limited by both MPn and labile carbon supply. Members of the generaAcidovorax,Rhodoferax, andAllorhizobium, organisms which make up less than 1% of Flathead Lake communities, consistently responded to MPn addition. We demonstrate that the genomic and physiological potential for MPn use exists among diverse, resident members of Flathead Lake and could contribute to OMP in freshwater lakes when substrates are available. IMPORTANCEMethane is an important greenhouse gas that is typically produced under anoxic conditions. We show that methane is supersaturated in a large oligotrophic lake despite the presence of oxygen. Metagenomic sequencing indicates that diverse, widespread microorganisms may contribute to the oxic production of methane through the cleavage of methylphosphonate. We experimentally demonstrate that these organisms, especially members of the genusAcidovorax, can produce methane through this process. However, appreciable rates of methane production only occurred when both methylphosphonate and labile sources of carbon were added, indicating that this process may be limited to specific niches and may not be completely responsible for methane concentrations in Flathead Lake. This work adds to our understanding of methane dynamics by describing the organisms and the rates at which they can produce methane through an oxic pathway in a representative oligotrophic lake. 

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5. Eutrophication and ice phenology influence methane storage in north temperate lakes

   https://doi.org/10.1002/lol2.70136  

   Wilkinson, Grace M; McCarthy, Moira; Bertolet, Brittni; Carpenter, Stephen R; Ha, Dat; Lottig, Noah; Szydlowski, Daniel K; Pace, Michael L; Jones, Stuart (May 2026, Limnology and Oceanography Letters)

   Abstract Among lakes, eutrophication is positively related to methane emissions, but various processes can alter the seasonal conversion of primary production into stored methane. We used a series of whole‐lake enrichment and shading experiments across three years with varying ice phenology to assess how eutrophication and ice cover affect within‐year methane storage. The seasonal pattern of methane storage was driven in part by cyanobacteria blooms and their influence on light and oxygen availability. Early ice‐off reduced anoxic volume and methane storage in both the manipulated and reference lake, but a subsequent bloom and shading in the manipulated lake drove a rapid increase in methane, with storage reaching similar levels to those of other years. These experiments revealed that interactions between ice phenology and eutrophication can drive shifts in seasonal methane storage trajectories in north temperate lakes. Improved understanding of variability in these drivers could substantially reduce uncertainty in lake methane emissions. 

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