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1. Effects of pH and Ca exchange on the structure and redox state of synthetic Na-birnessite

   https://doi.org/10.2138/am-2020-7112  

   Elmi, Chiara ; Post, Jeffrey E. ; Heaney, Peter J. ; Ilton, Eugene S. ( January 2021 , American Mineralogist)

   null (Ed.)

   Abstract Birnessite-like minerals are among the most common Mn oxides in surficial soils and sediments, and they mediate important environmental processes (e.g., biogeochemical cycles, heavy metal confinement) and have novel technological applications (e.g., water oxidation catalysis). Ca is the dominant interlayer cation in both biotic and abiotic birnessites, especially when they form in association with carbonates. The current study investigated the structures of a series of synthetic Ca-birnessite analogs prepared by cation-exchange with synthetic Na-birnessite at pH values from 2 to 7.5. The resulting Ca-exchanged birnessite phases were characterized using powder X-ray diffraction and Rietveld refinement, Fourier transform infrared spectroscopy, Raman spectroscopy, X-ray photoelectron spectroscopy, and scanning and transmission electron microscopy. All samples synthesized at pH values greater than 3 exhibited a similar triclinic structure with nearly identical unit-cell parameters. The samples exchanged at pH 2 and 3 yielded hexagonal structures, or mixtures of hexagonal and triclinic phases. Rietveld structure refinement and X-ray photoelectron spectroscopy showed that exchange of Na by Ca triggered reduction of some Mn3+, generating interlayer Mn2+ and vacancies in the octahedral layers. The triclinic and hexagonal Ca-birnessite structures described in this study were distinct from Na- and H-birnessite, respectively. Therefore, modeling X-ray absorption spectra of natural Ca-rich birnessites through mixing of Na- and H-birnessite end-members will not yield an accurate representation of the true structure. 

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2. A century of change: Reconstructing the biogeochemical history of Hubbard Brook

   https://doi.org/10.1002/hyp.14256  

   Likens, Gene E. ; Buso, Donald C. ; Bernhardt, Emily S. ; Rosi, Emma ( June 2021 , Hydrological Processes)

   Ecosystems constantly adjust to altered biogeochemical inputs, changes in vegetation and climate, and previous physical disturbances. Such disturbances create overlapping ‘biogeochemical legacies’ affecting modern nutrient mass balances. To understand how ‘legacies’ affected watershed‐ecosystem (WEC) biogeochemistry during five decades of studies within the Hubbard Brook Experimental Forest (HBEF), we extended biogeochemical trends and hydrologic fluxes back to 1900 to provide an historical framework for our long‐term studies. This reconstruction showed acid rain peaking at HBEF in the late 1960s‐early 1970s near the beginning of the Hubbard Brook Ecosystem Study (HBES). The long‐term, parabolic arc in acid inputs to HBEF generated a corresponding arc in the ionic strength of stream water, with acid inputs generating increased losses of H⁺and soil base cations between 1963 and 1969 and then decreased losses after 1970. Nitrate release after disturbance is coupled with previous N‐deposition and storage, biological uptake, and hydrology. Sulfur was stored in soils from decades of acid deposition but is now nearly depleted. Total exports of base cations from the soil exchange pool represent one of the largest disturbances to forest and associated aquatic ecosystems at the HBEF since the Pleistocene glaciation. Because precipitation inputs of base cations currently are extremely small, such losses can only be replaced through the slow process of mineral weathering. Thus, the chemistry of stream water is extremely dilute and likely to become even more dilute than pre‐Industrial Revolution estimates. The importance of calculating chemical fluxes is clearly demonstrated in reconstruction of acid rain impacts during the pre‐measurement period. The aggregate impact of acid rain on WEC exports is far larger than historical forest harvest effects, and even larger than the most severe deforestation experiment (Watershed 2) at HBEF. A century of acid rain had a calcium stripping impact equivalent totwoW2 experiments involving complete deforestation and herbicide applications.

    

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3. 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)

   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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4. From on high: Geochemistry of alpine springs, Niwot Ridge, Colorado Front Range, USA

   https://doi.org/10.1002/hyp.13436  

   Fields, Jordan F. ; Dethier, David P. ( May 2019 , Hydrological Processes)

   Snowmelt‐fed springs and small (0.5 km²) upland catchments in alpine areas of the western United States contribute significantly to the quantity and inorganic chemistry of water delivered to downstream basins but have not been studied extensively. Mineral weathering, transit time, and hydrologic mixing control the solute chemistry of waters that drain the upland zone of Niwot Ridge, Colorado Front Range, and adjacent areas in the granitic core of the Southern Rocky Mountains. Water in 37 springs sampled in this study flows in generally short steep paths (~0.3 km) through shallow regolith with mean transit times (MTT) of weeks to months, producing solutions dominated by Si, Ca²⁺, Na⁺, and HCO₃⁻, locally SO₄²⁻. Rock type is a significant control on spring, surface, and shallow groundwater chemistry, and plagioclase (oligoclase) is the major source of dissolved Na⁺and Si. Concentrations of Ca²⁺exceed stoichiometric predictions of oligoclase weathering by ~3.5×; excess Ca²⁺likely represents weathering of aeolian material, vein calcite, or trace minerals. Concentrations of base cations and Si increase slowly with estimated MTT of 0.2 years for Niwot Ridge spring waters, and several years for shallow groundwater sampled by wells. Chemical weathering of silicate minerals is slow with estimated rates of ~2.0 and 0.2 pmol·m⁻²·s⁻¹for oligoclase and microcline, respectively; the most mineralized spring waters are saturated only with respect to kaolinite and montmorillonite. More than 50% of the dissolved base cations + Si measured in Boulder Creek at Orodell (~25 km downstream) accumulate before water emerges from alpine springs on Niwot Ridge. Warming global temperatures are shifting more high‐elevation precipitation to rain, potentially changing run‐off patterns, transit time, and solute loads. Acquisition of solutes by alpine waters thus has implications far beyond small upland catchments.

    

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5. Direct Evidence of Local pH Change and the Role of Alkali Cation during CO 2 Electroreduction in Aqueous Media

   https://doi.org/10.1002/anie.201912637  

   Zhang, Fen ; Co, Anne C. ( December 2019 , Angewandte Chemie International Edition)

   We report, for the first time, utilizing a rotating ring‐disc electrode (RRDE) assembly for detecting changes in the local pH during aqueous CO₂reduction reaction (CO₂RR). Using Au as a model catalyst where CO is the only product, we show that the CO oxidation peak shifts by −86±2 mV/pH during CO₂RR, which can be used to directly quantify the change in the local pH near the catalyst surface during electrolysis. We then applied this methodology to investigate the role of cations in affecting the local pH during CO₂RR and find that during CO₂RR to CO on Au in an MHCO₃buffer (where M is an alkali metal), the experimentally measured local basicity decreased in the order Li⁺> Na⁺> K⁺> Cs⁺, which agreed with an earlier theoretical prediction by Singh et al. Our results also reveal that the formation of CO is independent of the cation. In summary, RRDE is a versatile tool for detecting local pH change over a diverse range of CO₂RR catalysts. Additionally, using the product itself (i.e. CO) as the local pH probe allows us to investigate CO₂RR without the interference of additional probe molecules introduced to the system. Most importantly, considering that most CO₂RR products have pH‐dependent oxidation, RRDE can be a powerful tool for determining the local pH and correlating the local pH to reaction selectivity.

    

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