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Opis: Predicting variations in dissolved oxygen concentration (DO) is important for management and environmental monitoring of aquatic ecosystems. Regression analyses and univariate and multivariate time-series analyses based on autoregressive methods were performed to investigate oxygen conditions in the Pivka River, Slovenia. The monitoring site was established upstream where the river sinks into the karst cave Postojnska jama, which hosts one of the richest subterranean faunas yet studied worldwide. It was found that abnormal variations of DO started to be noticeable at values of DO < 3 mg/L and became more pronounced until the ecosystem reached fully anoxic conditions. The abnormal fluctuations during the critical summer period were due to environmental conditions, organic load and resident biota. Predictions for future detection of anomalies in DO values were made from stable residuals of the measured data, and it was demonstrated that the model could be used to obtain a reliable estimate for a short period, such as one day. The example presented an analysis pipeline based on specific and established threshold DO values, and it is particularly important for ecosystems with diversity hotspots where prolonged low DO values can pose a threat to their biota.
Ključne besede: karst (geology), aquatic ecosystems, dissolved oxygen, modelling, prediction
Objavljeno v RUNG: 05.09.2023; Ogledov: 359; Prenosov: 4
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Opis: Direct seawater electrolysis is key to massive hydrogen fuel production without the depletion of precious freshwater resources and the need for high-purity electrolytes. However, the presence of high-concentration chloride ions (Cl−) and alkaline-earth metal ions (Mg2+, Ca2+) poses great challenges to the stability and selectivity of the catalysts for seawater splitting. Here, we demonstrate a self-healing oxygen evolution reaction (OER) catalyst for long-term seawater electrolysis. By suppressing the competitive chlorine evolution reaction and precipitating the alkaline-earth metal ions through an alkaline treatment of the seawater, stable seawater oxidation is achieved owing to the self-healing ability of the borate-intercalated nickel–cobalt–iron oxyhydroxides (NiCoFe-Bi) OER catalyst under highly-alkaline conditions. The self-healing NiCoFe-Bi catalyst achieves stable seawater oxidation at a large current density of 500 mA cm−2 for 1000 h with near unity Faraday efficiency. Our results have demonstrated strong durability and high OER selectivity of the self-healing catalyst under harsh conditions, paving the way for industrial large-scale seawater electrolysis.
Ključne besede: chemistry, electrocatalysis, seawater oxidation, oxygen evolution reaction
Objavljeno v RUNG: 08.05.2023; Ogledov: 640; Prenosov: 0
Celotno besedilo (2,54 MB)

Opis: X-ray Raman spectroscopy (XRS) is an emerging spectroscopic technique that utilizes inelastic scattering of hard Xrays to study X-ray absorption edges of low Z elements in bulk material. It was used to identify and quantify the amount of carbonyl bonds in a cathode sample, in order to track the redox reaction inside metal−organic batteries during the charge/ discharge cycle. XRS was used to record the oxygen K-edge absorption spectra of organic polymer cathodes from different multivalent metal−organic batteries. The amount of carbonyl bond in each sample was determined by modeling the oxygen K-edge XRS spectra with the linear combination of two reference compounds that mimicked the fully charged and the fully discharged phases of the battery. To interpret experimental XRS spectra, theoretical calculations of oxygen K-edge absorption spectra based on density functional theory were performed. Overall, a good agreement between the amount of carbonyl bond present during different stages of battery cycle, calculated from linear combination of standards, and the amount obtained from electrochemical characterization based on measured capacity was achieved. The electrochemical mechanism in all studied batteries was confirmed to be a reduction of double carbonyl bond and the intermediate anion was identified with the help of theoretical calculations. X-ray Raman spectroscopy of the oxygen K-edge was shown to be a viable characterization technique for accurate tracking of the redox reaction inside metal−organic batteries.
Ključne besede: X-ray Raman spectroscopy, meta-organic batteries, oxygen K-edge XANES, electrochemical processes
Objavljeno v RUNG: 24.03.2022; Ogledov: 1350; Prenosov: 19
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Ključne besede: oxygen evolution reaction layered double hydroxide high current density degradation stability
Objavljeno v RUNG: 09.11.2021; Ogledov: 1523; Prenosov: 67
Celotno besedilo (12,80 MB)

Opis: The role of aqueous multiphase chemistry in the formation of secondary organic aerosol (SOA) remains difficult to quantify. We investigate it here by testing the rapid formation of moderate oxygen-to-carbon (O/C) SOA during a case study in Mexico City. A novel laboratory-based glyoxal-SOA mechanism is applied to the field data, and explains why less gas-phase glyoxal mass is observed than predicted. Furthermore, we compare an explicit gas-phase chemical mechanism for SOA formation from semi- and intermediate-volatility organic compounds (S/IVOCs) with empirical parameterizations of S/IVOC aging. The mechanism representing our current understanding of chemical kinetics of S/IVOC oxidation combined with traditional SOA sources and mixing of background SOA underestimates the observed O/C by a factor of two at noon. Inclusion of glyoxal-SOA with O/C of 1.5 brings O/C predictions within measurement uncertainty, suggesting that field observations can be reconciled on reasonable time scales using laboratory-based empirical relationships for aqueous chemistry.
Ključne besede: secondary organic aerosol, glyoxal, aqueous multiphase chemistry, oxygen-to-carbon ratio, single scattering albedo
Objavljeno v RUNG: 11.04.2021; Ogledov: 1738; Prenosov: 0
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