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1. Increased Biogenic Calcification and Burial Under Elevated p CO ₂ During the Miocene: A Model‐Data Comparison

   https://doi.org/10.1029/2022GB007541  

   Si, Weimin; Herbert, Timothy; Wu, Mengxi; Rosenthal, Yair (June 2023, Global Biogeochemical Cycles)

   Abstract Ocean acidification due to anthropogenic CO₂emission reduces ocean pH and carbonate saturation, with the projection that marine calcifiers and associated ecosystems will be negatively affected in the future. On longer time scale, however, recent studies of deep‐sea carbonate sediments suggest significantly increased carbonate production and burial in the open ocean during the warm Middle Miocene. Here, we present new model simulations in comparison to published Miocene carbonate accumulation rates to show that global biogenic carbonate production in the pelagic environment was approximately doubled relative to present‐day values when elevated atmosphericpCO₂led to substantial global warming ∼13–15 million years ago. Our analysis also finds that although high carbonate production was associated with high dissolution in the deep‐sea, net pelagic carbonate burial was approximately 30%–45% higher than modern. At the steady state of the long‐term carbon cycle, this requires an equivalent increase in riverine carbonate alkalinity influx during the Middle Miocene, attributable to enhanced chemical weathering under a warmer climate. Elevated biogenic carbonate production resulted in a Miocene ocean that had carbon (dissolved inorganic carbon) and alkalinity (total alkalinity) inventories similar to modern values but was poorly buffered and less saturated in both the surface and the deep ocean relative to modern. 

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2. Arctic Permafrost Thawing Enhances Sulfide Oxidation

   https://doi.org/10.1029/2022GB007644  

   Kemeny, Preston Cosslett; Li, Gen K.; Douglas, Madison; Berelson, William; Chadwick, Austin J.; Dalleska, Nathan F.; Lamb, Michael P.; Larsen, William; Magyar, John S.; Rollins, Nick E.; et al (November 2023, Global Biogeochemical Cycles)

   Abstract Permafrost degradation is altering biogeochemical processes throughout the Arctic. Thaw‐induced changes in organic matter transformations and mineral weathering reactions are impacting fluxes of inorganic carbon (IC) and alkalinity (ALK) in Arctic rivers. However, the net impact of these changing fluxes on the concentration of carbon dioxide in the atmosphere (pCO₂) is relatively unconstrained. Resolving this uncertainty is important as thaw‐driven changes in the fluxes of IC and ALK could produce feedbacks in the global carbon cycle. Enhanced production of sulfuric acid through sulfide oxidation is particularly poorly quantified despite its potential to remove ALK from the ocean‐atmosphere system and increasepCO₂, producing a positive feedback leading to more warming and permafrost degradation. In this work, we quantified weathering in the Koyukuk River, a major tributary of the Yukon River draining discontinuous permafrost in central Alaska, based on water and sediment samples collected near the village of Huslia in summer 2018. Using measurements of major ion abundances and sulfate () sulfur (³⁴S/³²S) and oxygen (¹⁸O/¹⁶O) isotope ratios, we employed the MEANDIR inversion model to quantify the relative importance of a suite of weathering processes and their net impact onpCO₂. Calculations found that approximately 80% of in mainstem samples derived from sulfide oxidation with the remainder from evaporite dissolution. Moreover,³⁴S/³²S ratios,¹³C/¹²C ratios of dissolved IC, and sulfur X‐ray absorption spectra of mainstem, secondary channel, and floodplain pore fluid and sediment samples revealed modest degrees of microbial sulfate reduction within the floodplain. Weathering fluxes of ALK and IC result in lower values ofpCO₂over timescales shorter than carbonate compensation (∼10⁴ yr) and, for mainstem samples, higher values ofpCO₂over timescales longer than carbonate compensation but shorter than the residence time of marine (∼10⁷ yr). Furthermore, the absolute concentrations of and Mg²⁺in the Koyukuk River, as well as the ratios of and Mg²⁺to other dissolved weathering products, have increased over the past 50 years. Through analogy to similar trends in the Yukon River, we interpret these changes as reflecting enhanced sulfide oxidation due to ongoing exposure of previously frozen sediment and changes in the contributions of shallow and deep flow paths to the active channel. Overall, these findings confirm that sulfide oxidation is a substantial outcome of permafrost degradation and that the sulfur cycle responds to permafrost thaw with a timescale‐dependent feedback on warming. 

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3. Primary to post‐depositional microbial controls on the stable and clumped isotope record of shoreline sediments at Fayetteville Green Lake

   https://doi.org/10.1111/gbi.12609  

   Leapaldt, Hanna C; Frantz, Carie M; Olsen‐Valdez, Juliana; Snell, Kathryn E; Trower, Elizabeth J; Ingalls, Miquela (July 2024, Geobiology)

   Abstract Lacustrine carbonates are a powerful archive of paleoenvironmental information but are susceptible to post‐depositional alteration. Microbial metabolisms can drive such alteration by changing carbonate saturationin situ, thereby driving dissolution or precipitation. The net impact these microbial processes have on the primary δ¹⁸O, δ¹³C, and Δ₄₇values of lacustrine carbonate is not fully known. We studied the evolution of microbial community structure and the porewater and sediment geochemistry in the upper ~30 cm of sediment from two shoreline sites at Green Lake, Fayetteville, NY over 2 years of seasonal sampling. We linked seasonal and depth‐based changes of porewater carbonate chemistry to microbial community composition, in situ carbon cycling (using δ¹³C values of carbonate, dissolved inorganic carbon (DIC), and organic matter), and dominant allochems and facies. We interpret that microbial processes are a dominant control on carbon cycling within the sediment, affecting porewater DIC, aqueous carbon chemistry, and carbonate carbon and clumped isotope geochemistry. Across all seasons and sites, microbial organic matter remineralization lowers the δ¹³C of the porewater DIC. Elevated carbonate saturation states in the sediment porewaters (Ω > 3) were attributed to microbes from groups capable of sulfate reduction, which were abundant in the sediment below 5 cm depth. The nearshore carbonate sediments at Green Lake are mainly composed of microbialite intraclasts/oncoids, charophytes, larger calcite crystals, and authigenic micrite—each with a different origin. Authigenic micrite is interpreted to have precipitated in situ from the supersaturated porewaters from microbial metabolism. The stable carbon isotope values (δ¹³C_carb) and clumped isotope values (Δ₄₇) of bulk carbonate sediments from the same depth horizons and site varied depending on both the sampling season and the specific location within a site, indicating localized (μm to mm) controls on carbon and clumped isotope values. Our results suggest that biological processes are a dominant control on carbon chemistry within the sedimentary subsurface of the shorelines of Green Lake, from actively forming microbialites to pore space organic matter remineralization and micrite authigenesis. A combination of biological activity, hydrologic balance, and allochem composition of the sediments set the stable carbon, oxygen, and clumped isotope signals preserved by the Green Lake carbonate sediments. 

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4. Carbonate uranium isotopes record global expansion of marine anoxia during the Toarcian Oceanic Anoxic Event

   https://doi.org/10.1073/pnas.2406032121  

   Remírez, Mariano N; Gilleaudeau, Geoffrey J; Gan, Tian; Kipp, Michael A; Tissot, François_L H; Kaufman, Alan J; Parente, Mariano (July 2024, Proceedings of the National Academy of Sciences)

   The Toarcian Oceanic Anoxic Event (T-OAE; ~183 Mya) was a globally significant carbon-cycle perturbation linked to widespread deposition of organic-rich sediments, massive volcanic CO₂release, marine faunal extinction, sea-level rise, a crisis in carbonate production related to ocean acidification, and elevated seawater temperatures. Despite recognition of the T-OAE as a potential analog for future ocean deoxygenation, current knowledge on the severity of global ocean anoxia is limited largely to studies of the trace element and isotopic composition of black shales, which are commonly affected by local processes. Here, we present the first carbonate-based uranium isotope (δ²³⁸U) record of the T-OAE from open marine platform limestones of the southeastern Tethys Ocean as a proxy for global seawater redox conditions. A significant negative δ²³⁸U excursion (~0.4‰) is recorded just prior to the onset of the negative carbon isotope excursion comprised within the T-OAE, followed by a long-lived recovery of δ²³⁸U values, thus confirming that the T-OAE represents a global expansion of marine anoxia. Using a Bayesian inverse isotopic mass balance model, we estimate that anoxic waters covered ~6 to 8% of the global seafloor during the peak of the T-OAE, which represents 28 to 38 times the extent of anoxia in the modern ocean. These data, combined with δ²³⁸U-based estimates of seafloor anoxic area for other CO₂-driven Phanerozoic OAEs, suggest a common response of ocean anoxia to carbon release, thus improving prediction of future anthropogenically induced ocean deoxygenation. 

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5. Fish Carbonates in the North Atlantic and Their Potential Role in the Carbon Cycle

   https://doi.org/10.1029/2024GB008387  

   Hashim, Mohammed S; Conte, Maureen H; Salter, Michael A; Pedrosa‐Pamies, Rut; Weber, J C; Hayden, Matthew G; Wilson, Rod W; Perry, Chris T; Crowley, Stephen F; Dennis, Paul F; et al (June 2025, Global Biogeochemical Cycles)

   Abstract Marine fish precipitate carbonates in their intestines that they subsequently excrete as part of an osmoregulatory strategy. While fish carbonates are proposed to be volumetrically significant to the global carbonate budget, no study has presented direct evidence of fish carbonates in the open ocean. Here we examine sediment trap material collected by the Oceanic Flux Program (OFP) in the North Atlantic and observe the episodic occurrence of enigmatic blue particles since 1992. The blue particles are comprised of calcite with unusually high magnesium content (up to 46 mol%) with distinctively depleted δ¹³C and enriched δ¹⁸O compared with calcite produced by common marine calcifiers. Based on the mineralogical, isotopic, and textural similarities between the blue particles and fish carbonates, we propose that the blue particles are produced by pelagic fish. Our data suggest that fish modify their intestinal fluids to create a concentrated, highly supersaturated,¹³C depleted solution capable of precipitating calcite with high magnesium content and low δ¹³C. Collectively, our data imply that fish carbonate production is an open‐ocean phenomenon, opening up the possibility that fish contribute to the production, dissolution, and export of carbonates globally. 

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