Browsing by Author "Fischer, Woodward W."

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    Arctic Permafrost Thawing Enhances Sulfide Oxidation
    (Wiley, 2023) 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.; Rowland, Joel; Smith, M. Isabel; Torres, Mark A.; Webb, Samuel M.; Fischer, Woodward W.; West, A. Joshua
    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 increase pCO2, 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 (SO42− {\textSO_4^2-\) 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 on pCO2. Calculations found that approximately 80% of SO42− {\textSO_4^2-\ 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 of pCO2 over timescales shorter than carbonate compensation (∼104 yr) and, for mainstem samples, higher values of pCO2 over timescales longer than carbonate compensation but shorter than the residence time of marine SO42− {\textSO_4^2-\ (∼107 yr). Furthermore, the absolute concentrations of SO42− {\textSO_4^2-\ and Mg2+ in the Koyukuk River, as well as the ratios of SO42− {\textSO_4^2-\ 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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    Balance and imbalance in biogeochemical cycles reflect the operation of closed, exchange, and open sets
    (National Academy of Sciences, 2024) Kemeny, Preston Cosslett; Torres, Mark A.; Fischer, Woodward W.; Blättler, Clara L.
    Biogeochemical reactions modulate the chemical composition of the oceans and atmosphere, providing feedbacks that sustain planetary habitability over geological time. Here, we mathematically evaluate a suite of biogeochemical processes to identify combinations of reactions that stabilize atmospheric carbon dioxide by balancing fluxes of chemical species among the ocean, atmosphere, and geosphere. Unlike prior modeling efforts, this approach does not prescribe functional relationships between the rates of biogeochemical processes and environmental conditions. Our agnostic framework generates three types of stable reaction combinations: closed sets, where sources and sinks mutually cancel for all chemical reservoirs; exchange sets, where constant ocean–atmosphere conditions are maintained through the growth or destruction of crustal reservoirs; and open sets, where balance in alkalinity and carbon fluxes is accommodated by changes in other chemical components of seawater or the atmosphere. These three modes of operation have different characteristic timescales and may leave distinct evidence in the rock record. To provide a practical example of this theoretical framework, we applied the model to recast existing hypotheses for Cenozoic climate change based on feedbacks or shared forcing mechanisms. Overall, this work provides a systematic and simplified conceptual framework for understanding the function and evolution of global biogeochemical cycles.
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    Riverine evidence for isotopic mass balance in the Earth’s early sulfur cycle
    (Springer Nature, 2018) Torres, Mark A.; Paris, Guillaume; Adkins, Jess F.; Fischer, Woodward W.
    During a time of negligible atmospheric pO2, Earth’s early sulfur cycle generated a spectacular geological signal seen as the anomalous fractionation of multiple sulfur isotopic ratios. The disappearance of this signal from the geologic record has been hypothesized to constrain the timing of atmospheric oxygenation, although interpretive challenges exist. Asymmetry in existing S isotopic data, for example, suggests that the Archaean crust was not mass balanced, with the implication that the loss of S isotope anomalies from the geologic record might lag the rise of atmospheric O2. Here, we present new S isotopic analyses of modern surface and groundwaters that drain Archaean terrains in order to independently evaluate Archaean S cycle mass balance. Natural waters contain sulfur derived from the underlying bedrock and thus can be used to ascertain its S isotopic composition at scales larger than typical geological samples allow. Analyses of 52 water samples from Canada and South Africa suggest that the Archaean crust was mass balanced with an average multiple S isotopic composition equivalent to the bulk Earth. Overall, our work supports the hypothesis that the disappearance of multiple S isotope anomalies from the sedimentary record provides a robust proxy for the timing of the first rise in atmospheric O2.