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Silicate weathering and organic carbon (OC) burial in soil regulate atmospheric CO2, but their influence on each other remains unclear. Generally, OC oxidation can generate acids that drive silicate weathering, yet clay minerals that form during weathering can protect OC and limit oxidation. This poses a conundrum where clay formation and OC preservation either compete or cooperate. Debate remains about their relative contributions because quantitative tools to simultaneously probe these processes are lacking while those that exist are often not measured in concert. Here we demonstrate that Li isotope ratios of sediment, commonly used to trace clay formation, can help constrain OC cycling. Measurements of river suspended sediment from two watersheds of varying physiography and analysis of published data from Hawaii soil profiles show negative correlations between solid-phase d7Li values and OC content, indicating the association of clay mineral formation with OC accumulation. Yet, the localities differ in their ranges of d7Li values and OC contents, which we interpret with a model of soil formation. We find that temporal trends of Li isotopes and OC are most sensitive to mineral dissolution/clay formation rates, where higher rates yield greater OC stocks and lower d7Li values. Whereas OC-enhanced dissolution primarily dictates turnover times of OC and silicate minerals, clay protection distinctly modifies soil formation pathways and is likely required to explain the range of observations. These findings underscore clay mineral formation, driven primarily by bedrock chemistry and secondarily by climate, as a principal modulator of weathering fluxes and OC accumulation in soil. 

Key Points We re‐evaluate equations proposed by Francis Hall to assess concentration‐discharge ( C ‐ Q ) relationships using newly available long‐term and high‐frequency data sets Across time steps we find that log‐log and log‐linear models perform equally well to describe C ‐ Q relationships Parametrization of storage‐discharge relationships via recession analyses provides additional insight to C ‐ Q relationships 

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.