Subsurface Oxygen Research Articles

Low temperature atomic layer deposition of PbO2 for electrochemical applications

A low temperature atomic layer deposition (ALD) process for PbO2was developed using bis(1-dimethylamino-2-methyl-2-propanolate)lead(II), Pb(DMAMP)2, and O3as the reactants, with a high growth rate of 2.6 Å/cycle. PbO2readily reduces under low oxygen partial pressures at moderate temperatures making it challenging to deposit ALD PbO2from Pb2+precursors. However, thin films deposited with this process showed small crystalline grains of α-PbO2and β-PbO2, without signs of reduced PbOxphases. The ALD PbO2thin films show the high electrical conductivity characteristic of bulk PbO2. In situ measurements of ALD PbO2film conductivity during growth suggest a reaction mechanism by which sub-surface oxygen mobility contributes to the growth of resistive PbO or PbOxduring the Pb(DMAMP)2surface reaction step, which is only fully oxidized from Pb2+to Pb4+during the O3reaction step. These films were electrochemically reduced to PbSO4in H2SO4and then reoxidized to PbO2, demonstrating their suitability for use as an electrode material for fundamental battery research and other electrochemical applications.

Size-Dependent Core-Shell Fine Structures and Oxygen Evolution Activity of Electrochemical IrOx Nanoparticles Revealed by Cryogenic Electron Microscopy.

Electrochemically oxidized amorphous iridium oxides (IrOx) offer significantly improved electrocatalytic activities on the oxygen evolution reaction (OER) compared to crystalline IrO2, yet the origin of their decent activity and their size-dependent properties have not been fully understood. An important argument is the formation of deprotonated oxygen species not only at the topmost surface but also at the near surface, which creates an electrophilic character that activates the OER electrocatalysis. However, high spatial resolution identification of the electrophilic oxygen species remains unachieved. We address this hitherto-unresolved problem on size-selected electrochemical IrOx nanoparticles (NPs) by using cryogenic scanning transmission electron microscopy combined with electron energy loss spectroscopy, which enables simultaneous atomic detection of the near surface compositional and electronic structures with minimal damage that are further correlated with their size-dependent OER activities. Depending on the particle size, the electrochemical IrOx NPs showed distinctly different core-shell fine structures ranging from amorphous and hydrous IrOxHy NPs to a "metallic Ir core/sub-stoichiometric IrOx interlayer/amorphous IrOxHy shell" NP structure. Moreover, the formation of deprotonated, electrophilic oxygen is directly identified at the substoichiometric IrOx interface layer. These features account for a previously unestablished particle size effect of the electrochemical IrOx NPs, showing increasing water oxidation reactivity with an increasing nanoparticle size. Our results provide important insights into how subsurface oxygen chemistry controls the surface reactivity in the nanoscale Ir-based OER electrocatalysts.

Observed APO Seasonal Cycle in the Pacific: Estimation of Autumn O2 Oceanic Emissions

AbstractIn this work, we investigated the seasonal cycle of atmospheric potential oxygen (APO), a unique tracer of air‐sea gas exchanges of molecular oxygen (O2) and carbon dioxide (CO2), expressed as APO = O2 + 1.1 × CO2. APO data were obtained from flask air samples collected since the late 1990s at three Japanese ground stations and on commercial cargo ships sailing between Japan and Australia/New Zealand, North America, and Southeast Asia. We also analyzed the APO spatial distribution and seasonal cycles with simulations from an atmospheric transport model using climatological oceanic O2 fluxes from an empirical product that relate O2 flux to ocean heat as input. Model simulations reproduced the observed APO seasonal cycles generally well, but with larger amplitudes and earlier occurrence of seasonal minima and maxima than in the observations. Moreover, the observed seasonal cycles exhibited larger APO enhancements than the simulations in autumn and early winter, especially in the North Pacific at 20°N–60°N. These enhancements remained when refining the comparison by adjusting the simulated APO peak‐to‐peak amplitudes and seasonal phases to the observations. This suggests additional O2 emissions in the North Pacific, not well expressed in the air‐sea O2 fluxes used as input for our model simulations. The average autumn enhancement at 40°N–60°N was approximately twice that measured at 20°N–40°N. Confirming previous studies, our results indicate two distinct mechanisms possibly contributing to the additional oceanic O2 emissions: outgassing from a subsurface shallow oxygen maximum at 20°N–40°N and autumn phytoplankton bloom at 40°N–60°N.

Can Subsurface Oxygen Species in Oxides Participate in Catalytic Reactions? An 17O Solid-State Nuclear Magnetic Resonance Study.

The impacts of subsurface species of catalysts on reaction processes are still under debate, largely due to a lack of characterization methods for distinguishing these species from the surface species and the bulk. By using 17O solid-state nuclear magnetic resonance (NMR) spectroscopy, which can distinguish subsurface oxygen ions in CeO2 (111) nanorods, we explore the effects of subsurface species of oxides in CO oxidation reactions. The intensities of the 17O NMR signals due to surface and subsurface oxygen ions decrease after the introduction of CO into CeO2 nanorods, with a more significant decrease observed for the latter, confirming the participation of subsurface oxygen species. Density functional theory calculations show that the reaction involves subsurface oxygen ions filling the surface oxygen vacancies created by the direct contact of surface oxygen with CO. This new approach can be extended to the study of the role of oxygen species in other catalytic reactions.

Subsurface oxygen at transition metal surfaces: Its direct atom-resolved imaging and role in metal oxidation

Clarifying how oxygen is incorporated into the subsurface region of metal surfaces is a crucial step towards a robust understanding of the initial oxidation of metals. Due to lack of direct atomic-resolution imaging of subsurface oxygen, the atomistic mechanisms of oxygen-metal interactions and the role of subsurface oxygen remain elusive. Here, by state-of-the-art transmission electron microscopy, we demonstrate a direct atom-resolved imaging of subsurface oxygen that is dissolved in the subsurface region of the Fe (001) and Ti (0001) surfaces. It is found that subsurface oxygen occupies the octahedral sites of the Fe and Ti lattices, rather than the tetrahedral sites. First-principles calculations reveal that the octahedral-site occupancy of subsurface oxygen is energetically more favorable compared to the tetrahedral-site occupancy and will facilitate the process of metal oxidation by reducing the formation energy of metal oxides. Our findings clarify the atomistic mechanism of how oxygen attacks metal surfaces for the initiation of oxidation that occurs everywhere in nature.

Towards detailed combustor wall kinetics: An experimental and kinetic modeling study of hydrogen oxidation on Inconel

Gas-phase hydrogen combustion is ubiquitous in industrial processes, and the associated surface kinetics on heat-resistant alloys plays a crucial role in designing efficient low-carbon technologies. We conducted new temperature programmed reduction experiments to determine the reducibility of materials following an oxidation cycle. These experiments were modeled using a thermoconsistent multi-site microkinetic model for H2 heterogeneous oxidation on Inconels, which was validated against literature experiments. This competitive adsorption model considers iron bulk content, hydrogen spillover and subsurface oxygen migration on hydrogen surface oxidation kinetics. New X-ray diffraction experiments confirmed the postulated crystallographic structures in the Inconel samples, suggesting their presence on the surface scale. The phenomenological model was coupled with several state-of-the-art gas-phase oxidation mechanisms to assess gas/surface reactions interaction as a function of material and temperature. The results reveal a complex interaction in which surface removes H radicals from the gas-phase, while the Bradford (H2+OH) reaction converts OH into H2O, promoting water adsorption on Inconel. This interaction was found to give rise to gas-phase thermokinetic oscillations. The model predicts a non-monotonous effect of reactor area-to-volume ratio on reactivity and emphasizes the impact of Inconel composition on product selectivity. Overall, the multi-site model provides new insight into the contrasting reactivities among active sites, bridging the gap between material science and heterogeneous combustion modeling.

Identifying the presence of subsurface oxygen on the Ti3C2 MXene using H2O as a probe molecule: A DFT study

Oxycarbide MXenes are two-dimensional transition metal carbides with subsurface oxygen content within their carbon layers. Substitutional oxygen atoms are thermodynamically very stable, impose virtually no lattice strain on their surroundings, and do not change the metallic behaviour of Ti3C2, making them very difficult to detect experimentally. Here, water is suggested as a probe to identify subsurface oxygen atoms on the H2-exposed and heat pre-treated Ti3C2 MXene. Independently of the oxygen concentration, density functional theory calculations show that water can adsorb near subsurface oxygen atoms as well as on stoichiometric Ti3C2 regions of the material and is deemed appropriate for identifying substitutional oxygen defects on Ti3C2 through frequency analysis. The calculated stretching mode of water increases by at least 67 cm−1 in the presence of subsurface oxygen, allowing the experimental detection of this defect, even at the lowest concentration considered, i.e., a replacement of 3 % of carbon by oxygen atoms.

Structure and Reactivity of Active Oxygen Species on Silver Surfaces for Ethylene Epoxidation.

The epoxidation of ethylene stands as one of the most important industrial catalytic reactions, and silver-based catalysts show superior activity and selectivity. Oxygen is activated on the surface of silver during the reaction and exerts a substantial impact on product selectivity. Notably, the oxygen species residing in the topmost atomic layers profoundly influence the reactivity of a catalyst. However, their characterization under in situ reaction conditions remains a huge challenge, and specific structures have not been identified yet. In this study, we employ in situ X-ray photoelectron spectroscopy and density functional theory calculations to determine the oxygen species formed at the topmost atomic layers of a silver foil and to assign them a structure. Three different groups of oxygen species activated on silver are identified: (i) surface lattice oxygen and two oxygen species originating from associatively adsorbed dioxygen and (ii) top and (iii) subsurface oxygen. Transient in situ photoelectron spectroscopy experiments are carried out to reveal the dynamic evolution and thus reactivity of the different oxygen species under ethylene epoxidation reaction environments. The top oxygen atom from the adsorbed associated dioxygen is the most active. Meanwhile, a frequency-selective data analysis method, developed to process time-resolved data, provides insights into the evolving trends of peak intensities for different oxygen species. The versatility of this method suggests its potential application in future time-resolved characterization studies.

Effect of surface composition on the stability of Ti- and V-based oxycarbide and oxynitride MXenes

Oxycarbide MXenes were recently experimentally identified, opening up the possibility of a vast majority of carbon-based MXenes synthesised to date being in fact oxycarbides, wherein some substitutional oxygen atoms are present amid the layers that were previously thought to contain carbon only. Here, using an approach based on density-functional theory, we study the structural, energetic and electronic properties of subsurface substitutional oxygen atoms on the X layers of MXenes of the form M2XT2, with M = Ti, V; X = C, N; and T = none, O or F. According to the calculations, subsurface O is thermodynamically stable in any concentration on all the analysed MXenes.Subsurface substitutional O atoms in the Ti2C MXene are thermodynamically driven towards the surface, leaving behind vacancies and creating local O surface terminations. Given that this process involves a very low energy barrier, we predict that, under conditions suitable for eliminating the surface termination of MXenes, many vacancies on the layers of X atoms should occur.The O-terminated carbide MXenes, Ti2CO2 and V2CO2, are stable with their hexagonal symmetry up to a threshold amount of subsurface O, around 75 %, which is above the maximum experimentally observed concentration, 65 %. The F surface termination stabilizes the hexagonal structure of MXenes, which no longer distort regardless of the presence and amount of subsurface oxygen. This suggests that MXene synthesis routes based on fluorine-containing compounds are the most indicated for synthesising nitride MXenes.The PBE functional predicts the semiconductor characteristics of the Ti2CO2 MXene to be lost in the presence of subsurface O, even a percentage as low as 6 %, the lowest considered in this work. The hybrid HSE06 functional predicts the oxycarbide material to remain a semiconductor, but with a significantly lowered band gap energy with increasing substitutional O content. Nevertheless, both functionals agree that the mixture of C and O atoms between the Ti layers of the Ti2CO2 MXene increases its conductivity. To the best of our knowledge, this MXene has never been confirmed experimentally to behave as a semiconductor probably because the real samples of this MXene contain subsurface oxygen.

Pd-induced polarized Cu0-Cu+ sites for electrocatalytic CO2-to-C2+ conversion in acidic medium

The acidic CO2 reduction reaction (CO2RR) offers a promising approach to mitigate CO2 reactant loss and carbonate deposition, which are challenging issues in alkaline or neutral electrolytes. However, the hydrogen evolution reaction (HER) competes in the proton-rich environment near the catalyst surface as a side reaction, reducing the energy efficiency of generating multi-carbon (C2+) products. In this work, we proposed a palladium (Pd) doping strategy in a copper (Cu)-based catalyst to stabilize polarized Cu0-Cu+ sites, thus enhancing the CC coupling step during the CO2RR while suppressing HER. At an optimal doping ratio of 6%, the Pd dopants were well dispersed as single atoms without aggregation, allowing for the stabilization of subsurface oxygen (OSub), preserving the polarized Cu0-Cu+ active sites, and reducing the energy barrier of CC coupling. The Pd-doped Cu/Cu2O catalyst exhibited a peak Faradaic efficiency (FE) of 64.0% for C2+ products with a corresponding C2+ partial current density of 407.1 mA∙cm−2 at −2.18 V versus a reversible hydrogen electrode, a high CO2 single-pass conversion efficiency (SPCE) of 73.2%, as well as a high electrochemical stability of ∼ 150 h at industrially relevant current densities, thus suggesting a potential approach for tuning the electrocatalytic CO2 performances in acidic environments with higher carbon conversion efficiencies.

Formation of the oxyl's potential energy surface by the spectral kinetics of a vibrational mode.

One of the most reactive intermediates for oxidative reactions is the oxyl radical, an electron-deficient oxygen atom. The discovery of a new vibration upon photoexcitation of the oxygen evolution catalysis detected the oxyl radical at the SrTiO3 surface. The vibration was assigned to a motion of the sub-surface oxygen underneath the titanium oxyl (Ti-O●-) created upon hole transfer to (or electron extraction from) a hydroxylated surface site. Evidence for such an interfacial mode is derived from its spectral shape, which exhibited a Fano resonance-a coupling of a sharp normal mode to continuum excitations. Here, this Fano resonance is utilized to derive precise formation kinetics of the oxyl radical and its associated potential energy surface (PES). From the Fano lineshape, the formation kinetics are obtained from the anti-resonance (the kinetics of the coupling factor), the resonance (the kinetics of the coupled continuum excitations), and the frequency integrated spectrum (the kinetics of the normal mode's cross-section). All three perspectives yield logistic function growth with a half-rise of 2.3 ± 0.3ps and a time constant of 0.48 ± 0.09ps. A non-equilibrium transient associated with photoexcitation is separated from the rise of the equilibrated PES. The logistic function characterizes the oxyl coverage at the very initial stages (t ∼ 0) to have an exponential growth rate that quickly decreases toward zero as a limiting coverage is reached. Such time-dependent reaction kinetics identify a dynamic activation barrier associated with the formation of a PES and quantify it for oxyl radical coverage.

Cross-shore transport and eddies promote large scale response to urban eutrophication

A key control on the magnitude of coastal eutrophication is the degree to which currents quickly transport nitrogen derived from human sources away from the coast to the open ocean before eutrophication develops. In the Southern California Bight (SCB), an upwelling-dominated eastern boundary current ecosystem, anthropogenic nitrogen inputs increase algal productivity and cause subsurface acidification and oxygen (O2\\documentclass[12pt]{minimal} \\usepackage{amsmath} \\usepackage{wasysym} \\usepackage{amsfonts} \\usepackage{amssymb} \\usepackage{amsbsy} \\usepackage{mathrsfs} \\usepackage{upgreek} \\setlength{\\oddsidemargin}{-69pt} \\begin{document}$$_{2}$$\\end{document}) loss along the coast. However, the extent of anthropogenic influence on eutrophication beyond the coastal band, and the physical transport mechanisms and biogeochemical processes responsible for these effects are still poorly understood. Here, we use a submesoscale-resolving numerical model to document the detailed biogeochemical mass balance of nitrogen, carbon and oxygen, their physical transport, and effects on offshore habitats. Despite management of terrestrial nutrients that has occurred in the region over the last 20 years, coastal eutrophication continues to persist. The input of anthropogenic nutrients promote an increase in productivity, remineralization and respiration offshore, with recurrent O2\\documentclass[12pt]{minimal} \\usepackage{amsmath} \\usepackage{wasysym} \\usepackage{amsfonts} \\usepackage{amssymb} \\usepackage{amsbsy} \\usepackage{mathrsfs} \\usepackage{upgreek} \\setlength{\\oddsidemargin}{-69pt} \\begin{document}$$_{2}$$\\end{document} loss and pH decline in a region located 30–90 km from the mainland. During 2013 to 2017, the spatially averaged 5-year loss rate across the Bight was 1.3 mmol m-3\\documentclass[12pt]{minimal} \\usepackage{amsmath} \\usepackage{wasysym} \\usepackage{amsfonts} \\usepackage{amssymb} \\usepackage{amsbsy} \\usepackage{mathrsfs} \\usepackage{upgreek} \\setlength{\\oddsidemargin}{-69pt} \\begin{document}$$^{-3}$$\\end{document} O2\\documentclass[12pt]{minimal} \\usepackage{amsmath} \\usepackage{wasysym} \\usepackage{amsfonts} \\usepackage{amssymb} \\usepackage{amsbsy} \\usepackage{mathrsfs} \\usepackage{upgreek} \\setlength{\\oddsidemargin}{-69pt} \\begin{document}$$_{2}$$\\end{document}, with some locations losing on average up to 14.2 mmol m-3\\documentclass[12pt]{minimal} \\usepackage{amsmath} \\usepackage{wasysym} \\usepackage{amsfonts} \\usepackage{amssymb} \\usepackage{amsbsy} \\usepackage{mathrsfs} \\usepackage{upgreek} \\setlength{\\oddsidemargin}{-69pt} \\begin{document}$$^{-3}$$\\end{document} O2\\documentclass[12pt]{minimal} \\usepackage{amsmath} \\usepackage{wasysym} \\usepackage{amsfonts} \\usepackage{amssymb} \\usepackage{amsbsy} \\usepackage{mathrsfs} \\usepackage{upgreek} \\setlength{\\oddsidemargin}{-69pt} \\begin{document}$$_{2}$$\\end{document}. The magnitude of loss is greater than model uncertainty assessed from data-model comparisons and from quantification of intrinsic variability. This phenomenon persists for 4 to 6 months of the year over an area of 278,40 km2\\documentclass[12pt]{minimal} \\usepackage{amsmath} \\usepackage{wasysym} \\usepackage{amsfonts} \\usepackage{amssymb} \\usepackage{amsbsy} \\usepackage{mathrsfs} \\usepackage{upgreek} \\setlength{\\oddsidemargin}{-69pt} \\begin{document}$$^{2}$$\\end{document} (∼\\documentclass[12pt]{minimal} \\usepackage{amsmath} \\usepackage{wasysym} \\usepackage{amsfonts} \\usepackage{amssymb} \\usepackage{amsbsy} \\usepackage{mathrsfs} \\usepackage{upgreek} \\setlength{\\oddsidemargin}{-69pt} \\begin{document}$$\\sim$$\\end{document}30% of SCB area). These recurrent features of acidification and oxygen loss are associated with cross-shore transport of nutrients by eddies and plankton biomass and their accumulation and retention within persistent eddies offshore within the SCB.

Thermal stratification and meromixis in four dilute temperate zone lakes

Abstract. Four adjacent lakes (Arco, Budd, Deming, and Josephine) within Itasca State Park in Minnesota, USA, are reported to be meromictic in the scientific literature. However, seasonally persistent chemoclines have never been documented. We collected seasonal profiles of temperature and specific conductance and placed temperature sensor chains in two lakes for ∼1 year to explore whether these lakes remain stratified through seasonal mixing events and what factors contribute to their stability. The results indicate that all lakes are predominantly thermally stratified and are prone to mixing in isothermal periods during spring and fall. Despite brief, semi-annual erosion of thermal stratification, Deming Lake showed no signs of complete mixing from 2006–2009 and 2019–2022 and is likely meromictic. However, the other lakes are not convincingly meromictic. Geochemical data indicate that water in Budd Lake, which contains the most water, is predominantly sourced from precipitation. The water in the other three lakes is of the calcium–magnesium–bicarbonate type, reflecting a source of water that has interacted with the deglaciated landscape. δ18OH2O and δ2HH2O measurements indicate the lakes are supplied by precipitation modified by evaporation. Josephine, Arco, and Deming lakes sit in a valley with likely permeable sediments and may be hydrologically connected through wetlands and recharged with shallow groundwater, as no streams are present. The water residence time in meromictic Deming Lake is short (100 d), yet it maintains a large reservoir of dissolved iron, indicating that shallow groundwater may be an additional source of water and dissolved ions. All four lakes develop subsurface chlorophyll maxima layers during the summer. All lakes also develop subsurface oxygen maxima that may result from oxygen trapping in the spring by rapidly developed summer thermoclines. Documenting the mixing status and general chemistry of these lakes enhances their utility and accessibility for future biogeochemical studies, which is important as lake stratification and anoxia are becoming more prevalent due to changes in climate and land use.

Square-pyramidal subsurface oxygen [Ag4OAg] drives selective ethene epoxidation on silver

Square-pyramidal subsurface oxygen [Ag4OAg] drives selective ethene epoxidation on silver

Effects of typhoons on primary production and dissolved oxygen in the East China Sea

Previous investigations confirm that typhoons deliver both dissolved oxygen and nutrient sources via promoting vertical/lateral exchanges between water masses. The former one replenishes oxygen for the bottom water and prevents persistent oxygen depletion, while the latter one facilitates primary production and subsequent subsurface oxygen consumption. However, it is left unknown if typhoons ultimately result in net gain or loss of dissolved oxygen during the passage. Tropical cyclone information, satellite observations, and numerical simulations were used to investigate the response of primary production and dissolved oxygen dynamics to typhoons. Results imply that both typhoon intensity, and distance between typhoon track and the Changjiang estuary control the magnitude of responses in primary production, air-sea oxygen flux, advection-induced oxygen variation, and oxygen consumption variation. The model-based oxygen budget analysis indicated that oxygen content increased after the passage of all typhoons occurred between 2011-2020. The findings in this study suggest that typhoons ultimately result in net gain of oxygen. The increased strength and frequency of typhoon in the warming future would play an important role in counteracting deoxygenation, which is likely to slow down the pace of deterioration of the seasonal hypoxia in this region.

Humic substances mediated superior photochemical pollutant conversion on defective TiO2 in environmentally relevant matrices: The key roles of oxygen vacancy in surface interactions, oxidant activation and radical generation

Ubiquitous humic substances usually exhibit strong interfering effects on target pollutant removal in advanced water purification. This work aims to develop a photochemical conversion system on the nonstoichiometric TiO2 for pollutant removal in environmentally relevant matrices. In this synergistic reaction system, the redox-reactive humic substances and defective oxygen vacancies can serve as the organic electron transfer mediator and the key surface reactive sites, respectively. This system achieves a superior pollutant degradation in real surface water at low oxidant concentrations. Reactive oxygen vacancies on the TiO2 surface and sub-surface are of considerable interest for this photochemical reaction system. By engineering defective oxygen vacancies on high-energy {001} polar facet, the surface and electronic interactions between tailored TiO2 and humic substances are greatly strengthened for the promoted electron transfer and oxidant activation. Rendered by the strong surface affinity and molecular activation, defective oxygen vacancies thermodynamically and dynamically promote reactive chain reactions for free radical formation, including the selective O2 reduction to ·O2− and the H2O2 activation to ·OH. Our findings take new insights into environmental geochemistry, and provide an effective strategy to in-situ boost the humic substances-mediated water purification without secondary pollution. Environmental implicationHumic substances are widely distributed in aquatic environment, thus playing important roles in environmental geochemistry. For example, humic substances can achieve good surface adsorption through electrostatic adsorption, ligand exchange and electronic interactions with typical TiO2 to form reactive ligand-metal charge transfer complexes for pollutant degradation. Inspired by the unique properties of surface and sub-surface oxygen vacancies, the defective TiO2 was designed to refine the humic substances-mediated photochemical reactions. A superior reactivity was measured for pollutant degradation. Our findings provide an effective strategy to boost naturally photochemical decontamination in environmentally relevant matrices.

Oxygen rise in the tropical upper ocean during the Paleocene-Eocene Thermal Maximum.

The global ocean's oxygen inventory is declining in response to global warming, but the future of the low-oxygen tropics is uncertain. We report new evidence for tropical oxygenation during the Paleocene-Eocene Thermal Maximum (PETM), a warming event that serves as a geologic analog to anthropogenic warming. Foraminifera-bound nitrogen isotopes indicate that the tropical North Pacific oxygen-deficient zone contracted during the PETM. A concomitant increase in foraminifera size implies that oxygen availability rose in the shallow subsurface throughout the tropical North Pacific. These changes are consistent with ocean model simulations of warming, in which a decline in biological productivity allows tropical subsurface oxygen to rise even as global ocean oxygen declines. The tropical oxygen increase may have helped avoid a mass extinction during the PETM.

Oxygen dynamics in a deep‐silled fjord: Tight coupling to the open shelf

AbstractOxygen is declining globally in subsurface seawater. Fjords are particularly susceptible to hypoxia, because entrance sills restrict water circulation. We studied the oxygen dynamics of the Kitimat Fjord System on the west coast of Canada, using 3 yr of data from moored sensors and water column profiles. Subsurface oxygen within the fjord system is principally controlled by the connection to Hecate Strait on the outer shelf. Variations in oxygen concentration in Hecate Strait are reflected in the water that is drawn into the fjord system year‐round at mid‐depth (50–150 m). Deep water is renewed annually, beginning in May/June. Remineralization results in a seasonal decline in oxygen at depth. In the absence of deep‐water renewal, the bottom water in the system could become hypoxic in 1–2 yr. Mixing over a shallow inner sill (100 m) replenishes the oxygen in the deep water of Gardner Canal year‐round. The decadal trends in oxygen concentration show an increase from the 1950s to a maximum in the late 1970s, followed by a decline through 2016. The decline over the period 1977–2016 is 0.018 mL L−1 yr−1 (~ 0.83 μmol L−1 yr−1), which is consistent with the decline observed over the upper continental shelf over the same period.

Characterizing Subsurface Oxygen Variability in the California Current System (CCS) and Its Links to Water Mass Distribution

AbstractThe california current system (CCS) supports a wide array of ecosystem services with hypoxia historically occurring in near‐bottom waters. Limited open ocean data coverage hinders the mechanistic understanding of CCS oxygen variability. By comparing three different models with varying horizontal resolutions, we found that dissolved oxygen (DO) anomalies in the CCS are propagated from shallower coastal areas to the deeper open ocean, where they are advected at a density and velocity consistent with basin‐scale circulation. Since DO decreases have been linked to water mass redistribution in the CCS, we conduct a water mass analysis on two of the models and on biogeochemical Argo floats that sampled multiple seasonal cycles. We found that high variability in biogeochemical variables (DO and nutrients) seen in regions of low variability of temperature and salinity could be linked to water mass mixing, as some of the water masses considered had higher gradients in biogeochemical variables compared to physical variables. Additional DO observations are needed, therefore, to further understand circulation changes in the CCS. We suggest that increased DO sampling north of 35˚N and near the shelf break would benefit model initialization and skill assessment, as well as allow for better assessment of the role of equatorial waters in driving DO in the northern CCS.

Rare Earth Evoked Subsurface Oxygen Species in Platinum Alloy Catalysts Enable Durable Fuel Cells.

Alleviating the degradation issue of Pt based alloy catalysts, thereby simultaneously achieving high mass activity and high durability in proton exchange membrane fuel cells (PEMFCs), is highly challenging. Herein, we provide a new paradigm to address this issue via delaying the place exchange between adsorbed oxygen species and surface Pt atoms, thereby inhibiting Pt dissolution, through introducing rare earth bonded subsurface oxygen atoms. We have succeeded in introducing Gd-O dipoles into Pt3 Ni via a high temperature entropy-driven process, with direct spectral evidence attained from both soft and hard X-ray absorption spectroscopies. The higher rated power of 0.93 W cm-2 and superior current density of 562.2 mA cm-2 at 0.8 V than DOE target for heavy-duty vehicles in H2 -air mode suggest the great potential of Gd-O-Pt3 Ni towards practical application in heavy-duty transportation. Moreover, the mass activity retention (1.04 A mgPt -1 ) after 40 k cycles accelerated durability tests is even 2.4 times of the initial mass activity goal for DOE 2025 (0.44 A mgPt -1 ), due to the weakened Pt-Oads bond interaction and the delayed place exchange process, via repulsive forces between surface O atoms and those in the sublayer. This work addresses the critical roadblocks to the widespread adoption of PEMFCs.