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Abstract In Clear Creek, which runs through the Iowa State University campus in Ames, Iowa, USA, several types of iron mineralisation occur within stagnant pools and slow-moving water. This includes rusty flocs, commonly observed in mineral springs, rust-stained sediments and iridescent films (‘schwimmeisen’) on the pool surfaces. Observations of iron mineralisation over the course of more than a year in a single reach indicated that mineralisation occurred after precipitation events once water levels in the stream had dropped. Iron extracted and quantified from Clear Creek sediments and pool waters indicated the stream and its sediments were unlikely to be supplying the iron for mineralisation. We hypothesise that the observed mineralisation could result from the discharge of shallow, reducing groundwater-bearing Fe(II) into stagnant pools that form in debris-dammed areas of the stream. Piezometers installed next to the creek documented that shallow groundwater contained dissolved Fe, with the source of Fe being the floodplain sediments and the hydraulic gradient promoted groundwater discharge into the stream. Microorganisms identified in mineralised pools using 16S rRNA amplicon sequencing revealed an elevated presence of putative iron-oxidizing and iron-reducing microorganisms in mineralised vs. non-mineralised pools. Further investigation of the iridescent films revealed them to be composed of amorphous Fe(III) minerals. We further hypothesise that microbial exudates reduce surface tension and potential micro-zones for subsequent microbial iron redox cycling with dissolved organic matter in the pools. Determining the processes controlling mineralisation can lead to a better understanding of the ecological role of iron mineralisation in agricultural watersheds and the importance of contaminant degradation and nutrient cycling. 

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. 

Abstract The greenhouse gas methane (CH4) contributed to a warm climate that maintained liquid water and sustained Earth’s habitability in the Precambrian despite the faint young sun. The viability of methanogenesis (ME) in ferruginous environments, however, is debated, as iron reduction can potentially outcompete ME as a pathway of organic carbon remineralization (OCR). Here, we document that ME is a dominant OCR process in Brownie Lake, Minnesota (midwestern United States), which is a ferruginous (iron-rich, sulfate-poor) and meromictic (stratified with permanent anoxic bottom waters) system. We report ME accounting for ≥90% and >9% ± 7% of the anaerobic OCR in the water column and sediments, respectively, and an overall particulate organic carbon loading to CH4 conversion efficiency of ≥18% ± 7% in the anoxic zone of Brownie Lake. Our results, along with previous reports from ferruginous systems, suggest that even under low primary productivity in Precambrian oceans, the efficient conversion of organic carbon would have enabled marine CH4 to play a major role in early Earth’s biogeochemical evolution. 

Abstract. Four adjacent lakes (Arco, Budd, Deming, and Josephine) within Itasca State Park in Minnesota, USA, are reported to be meromictic in the scientific literature. However, seasonally persistent chemoclines have never been documented. We collected seasonal profiles of temperature and specific conductance and placed temperature sensor chains in two lakes for ∼1 year to explore whether these lakes remain stratified through seasonal mixing events and what factors contribute to their stability. The results indicate that all lakes are predominantly thermally stratified and are prone to mixing in isothermal periods during spring and fall. Despite brief, semi-annual erosion of thermal stratification, Deming Lake showed no signs of complete mixing from 2006–2009 and 2019–2022 and is likely meromictic. However, the other lakes are not convincingly meromictic. Geochemical data indicate that water in Budd Lake, which contains the most water, is predominantly sourced from precipitation. The water in the other three lakes is of the calcium–magnesium–bicarbonate type, reflecting a source of water that has interacted with the deglaciated landscape. δ18OH2O and δ2HH2O measurements indicate the lakes are supplied by precipitation modified by evaporation. Josephine, Arco, and Deming lakes sit in a valley with likely permeable sediments and may be hydrologically connected through wetlands and recharged with shallow groundwater, as no streams are present. The water residence time in meromictic Deming Lake is short (100 d), yet it maintains a large reservoir of dissolved iron, indicating that shallow groundwater may be an additional source of water and dissolved ions. All four lakes develop subsurface chlorophyll maxima layers during the summer. All lakes also develop subsurface oxygen maxima that may result from oxygen trapping in the spring by rapidly developed summer thermoclines. Documenting the mixing status and general chemistry of these lakes enhances their utility and accessibility for future biogeochemical studies, which is important as lake stratification and anoxia are becoming more prevalent due to changes in climate and land use. 

Depth profiles of water column chemical and physical properties were assessed with seasonal-scale frequency from Little Comfort from September 2023 to June 2024 and from Keewahtin Lake in September 2023. The data were collected to assess mixing status, major geochemical constituents within the lake, and mineral precipitation reactions. Several parameters were routinely measured with deployable probes at meter or sub-meter resolution at the deepest location in each lake. Water samples were also collected for laboratory analysis. 

Depth profiles of water column chemical and physical properties were assessed with seasonal-scale frequency from four lakes in the Itasca State Park from 2006-2009 and from 2019-2023. The data was used to assess the mixing status and major geochemical constituents within the lakes. Several parameters were routinely measured with deployable probes at meter or sub-meter resolution at the deepest location in each lake. Water samples were also collected for laboratory analysis. Bathymetry data collected in 2022 is supplied as rasters. 

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.