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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. 

Land use and land cover (LULC) can significantly alter river water, which can in turn have important impacts on downstream coastal ecosystems by delivering nutrients that promote marine eutrophication and hypoxia. Well-documented in temperate systems, less is known about the way land cover relates to water quality in low-lying coastal zones in the tropics. Here we evaluate the catchment LULC and the physical and chemical characteristics of six rivers that contribute flow into a seasonally hypoxic tropical bay in Bocas del Toro, Panama. From July 2019 to March 2020, we routinely surveyed eight physical and chemical characteristics (temperature, specific conductivity, salinity, pH, dissolved oxygen (DO), nitrate and nitrite, ammonium, and phosphate). Our goals were to determine how these physical and chemical characteristics of the rivers reflect the LULC, to compare the water quality of the focal rivers to rivers across Panama, and to discuss the potential impacts of river discharge in the Bay. Overall, we found that the six focal rivers have significantly different river water characteristics that can be linked to catchment LULC and that water quality of rivers 10 s of kilometers apart could differ drastically. Two focal catchments dominated by pristine peat swamp vegetation in San San Pond Sak, showed characteristics typical of blackwater rivers, with low pH, dissolved oxygen, and nutrients. The remaining four catchments were largely mountainous with >50% forest cover. In these rivers, variation in nutrient concentrations were associated with percent urbanization. Comparisons across Panamanian rivers covered in a national survey to our focal rivers shows that saltwater intrusions and low DO of coastal swamp rivers may result in their classification by a standardized water quality index as having slightly contaminated water quality, despite this being their natural state. Examination of deforestation over the last 20 years, show that changes were <10% in the focal catchments, were larger in the small mountainous catchments and suggest that in the past 20 years the physical and chemical characteristics of river water that contributes to Almirante Bay may have shifted slightly in response to these moderate land use changes. (See supplementary information for Spanish-language abstract). 

Basaltic watersheds such as those found in Iceland are thought to be important sites of CO₂sequestration via silicate weathering. However, determining the magnitude of CO₂uptake depends on accurately interpreting river chemistry. Here, we compile geochemical data from Iceland and use them to constrain weathering processes. Specifically, we use a newly developed inverse model to quantify solute supply from rain and hydrothermal fluids as well as allow for variable silicate end‐member compositions, solutes to be removed via secondary phase formation, and some Ca to be sourced from carbonate dissolution. While some of these processes have been considered previously, they have not been considered together allowing us to newly determine their relative contributions. We find that weathering in Iceland is incongruent in two ways. First, solute release from primary silicates is characterized by a higher proportion of Na than would be expected from bulk basalts, which may reflect preferential weathering or some contribution from rhyolites. This Na enrichment is further enhanced by preferential Mg and K uptake by secondary phases. No samples in our data set (n = 537) require carbonate dissolution even if isotopic data (δ²⁶Mg,δ³⁰Si,δ⁴⁴Ca, and/or⁸⁷Sr/⁸⁶Sr) are included. While some carbonate weathering is allowable, silicate weathering likely dominates. The complexity we observe in Iceland underscores the need for inverse models to account for a wide range of processes and end‐members. Given that riverine fluxes from Iceland are more Na‐rich than expected for congruent basalt weathering, the characteristic timescale of CO₂drawdown is likely affected.

 

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.

 

Silicate minerals represent an important reservoir of nutrients at Earth's surface and a source of alkalinity that modulates long‐term geochemical cycles. Due to the slow kinetics of primary silicate mineral dissolution and the potential for nutrient immobilization by secondary mineral precipitation, the bioavailability of many silicate‐bound nutrients may be limited by the ability of micro‐organisms to actively scavenge these nutrients via redox alteration and/or organic ligand production. In this study, we use targeted laboratory experiments with olivine and the siderophore deferoxamine B to explore how microbial ligands affect nutrient (Fe) release and the overall rate of mineral dissolution. Our results show that olivine dissolution rates are accelerated in the presence of micromolar concentrations of deferoxamine B. Based on the non‐linear decrease in rates with time and formation of a Fe³⁺‐ligand complex, we attribute this acceleration in dissolution rates to the removal of an oxidized surface coating that forms during the dissolution of olivine at circum‐neutralpHin the presence of O₂and the absence of organic ligands. While increases in dissolution rates are observed with micromolar concentrations of siderophores, it remains unclear whether such conditions could be realized in natural environments due to the strong physiological control on microbial siderophore production. So, to contextualize our experimental results, we also developed a feedback model, which considers how microbial physiology and ligand‐promoted mineral dissolution kinetics interact to control the extent of biotic enhancement of dissolution rates expected for different environments. The model predicts that physiological feedbacks severely limit the extent to which dissolution rates may be enhanced by microbial activity, though the rate of physical transport modulates this limitation.