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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. 

Organic carbon (OC) sedimentation in marine sediments is the largest long‐term sink of atmospheric CO2 after silicate weathering. Understanding the mechanistic and quantitative aspects of OC delivery and preservation in marine sediments is critical for predicting the role of the oceans in modulating global climate. Yet, estimates of the global OC sedimentation in marginal settings span an order of magnitude, and the primary controls of OC preservation remain highly debated. Here, we provide the first global bottom‐up estimate of OC sedimentation along the margins using a synthesis of literature data. We quantify both terrestrial‐ and marine‐sourced OC fluxes and perform a statistical analysis to discern the key factors influencing their magnitude. We find that the margins host 23.2 ± 3.5 Tmol of OC sedimentation annually, with approximately 84% of marine origin. Accordingly, we calculate that only 2%–3% of OC exported from the euphotic zone escapes remineralization before sedimentation. Surprisingly, over half of all global OC sedimentation occurs below bottom waters with oxygen concentrations greater than 180 μM, while less than 4% occurs in settings with <50 μM oxygen. This challenges the prevailing paradigm that bottom‐water oxygen (BWO) is the primary control on OC preservation. Instead, our statistical analysis reveals that water depth is the most significant predictor of OC sedimentation, surpassing all other factors investigated, including BWO levels and sea‐surface chlorophyll concentrations. This finding suggests that the primary control on OC sedimentation is not production, but the ability of OC to resist remineralization during transit through the water column and while settling on the seafloor. 

These data correspond to the article “Deep Nitrogen Fluxes and Sources Constrained by Arc Lava Phenocrysts” by Hudak et al. submitted to Geophysical Research Letters. Table S1 includes N-He-Ar data for FIs in phenocrysts from mafic are lavas and tephras. Table S2 contains the corrected N2/3He data used for volcanic arc N flux calculations and the arc-averaged mean N arc flux. Table S3 summarizes previous literature estimates of N fluxes and the data used for those calculations. Table S4 provides the N concentrations, He concentrations, N isotope compositions of the mantle, sediments, and altered oceanic crust, as well as sediment thicknesses. Finally, Table S5 gives information about the sources of the mineral separates used for these analyses. 

Mantle-derived, low-degree melts, such as kimberlites, carbonate-rich olivine lamproites (CROLS), and cratonic olivine lamproites, are the main carriers of diamonds. They are rare ultramafic, volatile-rich volcanic magmas, generally restricted to stable cratons, and are the deepest-sourced magmas erupted onto Earth’s surface. As hybrid magmas, their formation mechanism and mantle sources remain enigmatic and highly debated, especially the nature of the processes leading to their “enriched” isotopic signatures. The often extreme isotopic compositions of Sr, Nd, Pb, and Hf suggest that the mantle sources of these magmas vary between an ancient and geochemically depleted component and various enriched components. The enriched components could include crustal material recycled into the convective mantle or metasomatized lithospheric mantle. For the latter, discriminating between assimilation by sub-lithospheric magmas during the ascent or melting of element-enriched material from within the lithospheric mantle is paramount concerning petrogenesis. As the stable isotope composition of K, and Ba vary between surface and mantle reservoirs, they are well-suited tools for addressing the cause of different radiogenic isotopic signatures and to better constrain the mantle sources of these important magmas. Here, we use collision cell multi-collector inductively-coupled-plasma mass-spectrometry (MC-ICP-MS) and traditional MC-ICP-MS to conduct the first comprehensive whole-rock K and Ba stable isotope study on a wide range of low-degree mantle-derived melts. All the deep-seated, low-degree melts analyzed here show no correlation between melting/differentiation indices and δ41K and δ138Ba compositions, implying that any isotopic fractionation during melting or eruption was limited and that the different mantle and crustal reservoirs affecting these melts dominate their isotopic variability. Overall, kimberlites show limited δ41K and δ138Ba variability, with a median δ41K of -0.40 ± 0.06‰ (2SE) and δ138Ba of 0.00 ± 0.07‰ (2SE), within error relative to an estimated bulk silicate Earth [(BSE: δ41K= -0.42±0.07‰ (2SD) and δ138Ba=0.03±0.04‰ (2SD)], suggesting significant sublithospheric input. While the sample size is small (N=4), Canadian kimberlites from Lake De Gras display a bi-modal distribution with δ41K values slightly higher and lower relative to BSE, ascribed to crustal and lithospheric contamination. Like kimberlites, South African CROLS show limited K isotope variability with a median δ41K of -0.48 ± 0.02‰ (2SE). Their compositions are non-resolvable from two Mica-Amphibole-Rutile-Ilmenite-Diopside (MARID) xenoliths. The δ138Ba of the CROLS also shows limited variation with a median δ138Ba of 0.00 ± 0.07‰ (2SE), plotting within BSE estimations. Compared to the other low-degree mantle-derived melts, cratonic olivine/leucite-bearing lamproites from West Australia show a wide range in δ41K (-0.97‰ to +0.34‰) and δ138Ba (-0.30‰ to +0.27) values. The observed large K isotopic variation in cratonic lamproites is similar to that observed in post-collisional lamproites and is ascribed to sediment recycling. Argyle lamproites define robust correlations between potassium and barium elemental abundances, and their stable isotopes call for significant hydrothermal fluid-assisted leaching and isotopic fractionation. 

Cadmium (Cd) has a nutrient-like distribution in the ocean, similar to the macronutrient phosphate. Significant isotope fractionation induced by the biological cycling of Cd makes it a potential tracer for nutrients and productivity. However, the Cd flux and Cd isotope composition of marine sediments may also be influenced by local redox conditions and partial remineralization of organically hosted Cd. These confounding factors are under-constrained and render it challenging to use Cd as a reliable paleoproxy. To understand the relative importance of each of these processes, we examined the Cd isotope systematics of 69 modern sediments deposited across a wide range of environments. We complement these data with four profiles of particulate Cd isotope compositions from the Southern Ocean. We report three main results. First, we show that the sedimentary flux of Cd is tightly coupled to that of organic matter. Second, most Cd burial occurs in regions with some bottom-water oxygen, and the flux of CdS to anoxic regions is, globally, minor. Finally, we find that remineralization can substantially modify sedimentary Cd isotope compositions, though it is challenging to relate pelagic and sedimentary processes. For example, we find that the relationship between sedimentary Cd isotope compositions and surface seawater [Cd] is the reverse of that predicted by isotope reactor models. Likewise, sedimentary Cd isotope compositions are anti-correlated with bottom-water oxygen. While this pattern is consistent with preferential remineralization of isotopically heavy Cd, profiles of marine particulate matter reveal the reverse, whereby the Cd isotope composition of large particles, which are most likely to reach the seafloor, becomes increasingly ‘heavy’ with depth. These results highlight how productivity, redox, and remineralization all influence the flux and isotope composition of Cd to marine sediments. While our study suggests that there is no simple way to relate sedimentary Cd isotopes to surface nutrient utilization, our data point toward several potential controls that could form the basis of novel proxies for local redox conditions and remineralization.