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Continuous greenhouse gas monitoring at sub-zero temperatures is needed for monitoring greenhouse gas emission in cold environments such as the Arctic tundra. This work reports a single-frequency electrochemical impedance sensing (SF-EIS) method for real-time continuous monitoring of carbon dioxide (CO2) at a wide range of temperatures (−15 to 40 °C) by using robust ionic liquid (IL) sensing materials and noninvasive, low-power, and low-cost impedance readout mechanisms since they cause minimal changes in the sensing interface, avoiding the baseline change for long-term continuous sensing. In addition, a miniaturized planar electrochemical sensor was fabricated that incorporates a hydrophobic 1-butyl-1-methylpyrrolidinium bis(trifluromethylsulfonyl)imide ([Bmpy][NTf2]) IL electrolyte and Pt black electrode materials. The high viscosity of the ILs facilitates the formation of thin, ordered, and concentrated layers of ionic charges, and the inverse relationship of IL viscosity with temperature makes them especially suited for impedance sensing at low temperatures. The unique low-temperature properties of ILs together with EIS transduction mechanisms are shown to be sensitive and selective for continuously monitoring CO2 at a −15 to 40 °C temperature range via impedance changes at a specifically selected frequency at the open circuit potential (OCP). Molecular dynamics simulations revealed insights into the structure and dynamics of the IL at varying temperatures in the presence of methane and CO2 and provided potential explanations for the observed sensing results. The miniaturized and flexible planar electrochemical sensor with the [Bmpy][NTf2] electrolyte was tested repeatedly at subzero temperatures over a 58-day period, during which good stability and repeatability were obtained. The CO2 impedance sensor was further tested for sensing CO2 from soil samples and shows promising results for their use in real-time monitoring of greenhouse gas emissions in cold temperatures such as permafrost soils.more » « less
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Examples of anaerobic oxidation of aldehydes in hydrothermal solutions are reported. The reaction using iron( iii ) nitrate as the oxidant occurs under mild hydrothermal conditions and generates carboxylic acids in good yields. This method differs from previous studies which use atmospheric oxygen as the oxidant.more » « less
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Abstract Natural organic matter plays an important role in oceanic hydrothermal systems through a combination of geological and chemical processes. However, identifying the hydrothermal pathways of organic compounds is still quite limited, preventing us from understanding how organic matter is transformed in hydrothermal systems. In this study, we focus on the reaction pathways of alkenes, which represent a key functional group intermediate linking the most abundant hydrocarbons in seafloor hydrothermal environments. Three major pathways are observed for alkenes under mild hydrothermal conditions, including hydration, oxidation, and dimerization. The pathway distributions of alkenes can be affected by the presence of dissolved metal salts; hydration of alkenes is driven by metal ions via the change of solution pH, while alkene dimerization is controlled by pH and the type of metal cations and complexes. Overall, this study identifies alkene hydrothermal pathways and highlights the important roles of metal salts in controlling hydrothermal transformations.more » « less
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