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1. Global reconstruction reduces the uncertainty of oceanic nitrous oxide emissions and reveals a vigorous seasonal cycle

   https://doi.org/10.1073/pnas.1921914117  

   Yang, Simon; Chang, Bonnie X.; Warner, Mark J.; Weber, Thomas S.; Bourbonnais, Annie M.; Santoro, Alyson E.; Kock, Annette; Sonnerup, Rolf E.; Bullister, John L.; Wilson, Samuel T.; et al (May 2020, Proceedings of the National Academy of Sciences)

   Assessment of the global budget of the greenhouse gas nitrous oxide ( ${\mathrm{N}}_2$O) is limited by poor knowledge of the oceanic ${\mathrm{N}}_2$O flux to the atmosphere, of which the magnitude, spatial distribution, and temporal variability remain highly uncertain. Here, we reconstruct climatological ${\mathrm{N}}_2$O emissions from the ocean by training a supervised learning algorithm with over 158,000 ${\mathrm{N}}_2$O measurements from the surface ocean—the largest synthesis to date. The reconstruction captures observed latitudinal gradients and coastal hot spots of ${\mathrm{N}}_2$O flux and reveals a vigorous global seasonal cycle. We estimate an annual mean ${\mathrm{N}}_2$O flux of 4.2 ± 1.0 Tg N $\cdot {\mathrm{y}}^{-1}$, 64% of which occurs in the tropics, and 20% in coastal upwelling systems that occupy less than 3% of the ocean area. This ${\mathrm{N}}_2$O flux ranges from a low of 3.3 ± 1.3 Tg N $\cdot {\mathrm{y}}^{-1}$in the boreal spring to a high of 5.5 ± 2.0 Tg N $\cdot {\mathrm{y}}^{-1}$in the boreal summer. Much of the seasonal variations in global ${\mathrm{N}}_2$O emissions can be traced to seasonal upwelling in the tropical ocean and winter mixing in the Southern Ocean. The dominant contribution to seasonality by productive, low-oxygen tropical upwelling systems (>75%) suggests a sensitivity of the global ${\mathrm{N}}_2$O flux to El Niño–Southern Oscillation and anthropogenic stratification of the low latitude ocean. This ocean flux estimate is consistent with the range adopted by the Intergovernmental Panel on Climate Change, but reduces its uncertainty by more than fivefold, enabling more precise determination of other terms in the atmospheric ${\mathrm{N}}_2$O budget. 

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2. Theoretical Analysis of Critical Conditions for Crack Formation and Propagation, and Optimal Operation of SOECs

   https://doi.org/10.1149/1945-7111/ac5fee  

   Wang, Yudong; Virkar, Anil V.; Khonsari, M. M.; Zhou, Xiao-Dong (April 2022, Journal of The Electrochemical Society)

   A theoretical analysis on crack formation and propagation was performed based on the coupling between the electrochemical process, classical elasticity, and fracture mechanics. The chemical potential of oxygen, thus oxygen partial pressure, at the oxygen electrode-electrolyte interface ( ${\mu }_{O_2}^{\mathit{OE\mid El}}$) was investigated as a function of transport properties, electrolyte thickness and operating conditions (e.g., steam concentration, constant current, and constant voltage). Our analysis shows that: a lower ionic area specific resistance (ASR), $r_i^{OE},$and a higher electronic ASR ( $r_e^{OE}$) of the oxygen electrode/electrolyte interface are in favor of suppressing crack formation. The ${\mu }_{O_2}^{OE\mid El},$thus local pO₂, are sensitive towards the operating parameters under galvanostatic or potentiostatic electrolysis. Constant current density electrolysis provides better robustness, especially at a high current density with a high steam content. While constant voltage electrolysis leads to greater variations of ${\mu }_{O_2}^{OE\mid El}.$Constant current electrolysis, however, is not suitable for an unstable oxygen electrode because ${\mu }_{O_2}^{OE\mid El}$can reach a very high value with a gradually increased $r_i^{OE}.$A crack may only occur under certain conditions when $p_{O_2}^{TPB}>p_{cr}.$ 

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3. Keck Planet Imager and Characterizer Emission Spectroscopy of WASP-33b

   https://doi.org/10.3847/1538-3881/acda91  

   Finnerty, Luke; Schofield, Tobias; Sappey, Ben; Xuan, Jerry W.; Ruffio, Jean-Baptiste; Wang, Jason J.; Delorme, Jacques-Robert; Blake, Geoffrey A.; Buzard, Cam; Fitzgerald, Michael P.; et al (June 2023, The Astronomical Journal)

   Abstract We present Keck Planet Imager and Characterizer (KPIC) high-resolution (R∼35,000)K-band thermal emission spectroscopy of the ultrahot Jupiter WASP-33b. The use of KPIC’s single-mode fibers greatly improves both blaze and line-spread stabilities relative to slit spectrographs, enhancing the cross-correlation detection strength. We retrieve the dayside emission spectrum with a nested-sampling pipeline, which fits for orbital parameters, the atmospheric pressure–temperature profile, and the molecular abundances. We strongly detect the thermally inverted dayside and measure mass-mixing ratios for CO ( ${\mathrm{logCO}}_{\mathrm{MMR}}=-{1.1}_{-0.6}^{+0.4}$), H₂O ( ${\mathrm{logH}}_2{\mathrm{O}}_{\mathrm{MMR}}=-{4.1}_{-0.9}^{+0.7}$), and OH ( ${\mathrm{logOH}}_{\mathrm{MMR}}=-{2.1}_{-1.1}^{+0.5}$), suggesting near-complete dayside photodissociation of H₂O. The retrieved abundances suggest a carbon- and possibly metal-enriched atmosphere, with a gas-phase C/O ratio of ${0.8}_{-0.2}^{+0.1}$, consistent with the accretion of high-metallicity gas near the CO₂snow line and post-disk migration or with accretion between the soot and H₂O snow lines. We also find tentative evidence for¹²CO/¹³CO ∼ 50, consistent with values expected in protoplanetary disks, as well as tentative evidence for a metal-enriched atmosphere (2–15 × solar). These observations demonstrate KPIC’s ability to characterize close-in planets and the utility of KPIC’s improved instrumental stability for cross-correlation techniques. 

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4. Stabilizing Ti ₃ C ₂ T _x MXene flakes in air by removing confined water

   https://doi.org/10.1073/pnas.2400084121  

   Fang, Hui; Thakur, Anupma; Zahmatkeshsaredorahi, Amirhossein; Fang, Zhenyao; Rad, Vahid; Shamsabadi, Ahmad A; Pereyra, Claudia; Soroush, Masoud; Rappe, Andrew M; Xu, Xiaoji G; et al (July 2024, Proceedings of the National Academy of Sciences)

   MXenes have demonstrated potential for various applications owing to their tunable surface chemistry and metallic conductivity. However, high temperatures can accelerate MXene film oxidation in air. Understanding the mechanisms of MXene oxidation at elevated temperatures, which is still limited, is critical in improving their thermal stability for high-temperature applications. Here, we demonstrate that Ti ${}_3$C ${}_2$T ${}_x$MXene monoflakes have exceptional thermal stability at temperatures up to 600 ${}^{°}$C in air, while multiflakes readily oxidize in air at 300 ${}^{°}$C. Density functional theory calculations indicate that confined water between Ti ${}_3$C ${}_2$T ${}_x$flakes has higher removal energy than surface water and can thus persist to higher temperatures, leading to oxidation. We demonstrate that the amount of confined water correlates with the degree of oxidation in stacked flakes. Confined water can be fully removed by vacuum annealing Ti ${}_3$C ${}_2$T ${}_x$films at 600 ${}^{°}$C, resulting in substantial stability improvement in multiflake films (can withstand 600 ${}^{°}$C in air). These findings provide fundamental insights into the kinetics of confined water and its role in Ti ${}_3$C ${}_2$T ${}_x$oxidation. This work enables the use of stable monoflake MXenes in high-temperature applications and provides guidelines for proper vacuum annealing of multiflake films to enhance their stability. 

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5. Structural phase purification of bulk HfO ₂ :Y through pressure cycling

   https://doi.org/10.1073/pnas.2312571121  

   Musfeldt, J. L.; Singh, Sobhit; Fan, Shiyu; Gu, Yanhong; Xu, Xianghan; Cheong, S.-W.; Liu, Z.; Vanderbilt, David; Rabe, Karin M. (January 2024, Proceedings of the National Academy of Sciences)

   We combine synchrotron-based infrared absorption and Raman scattering spectroscopies with diamond anvil cell techniques and first-principles calculations to explore the properties of hafnia under compression. We find that pressure drives HfO ${}_2$:7%Y from the mixed monoclinic ( $P{2}_1/c$) $+$antipolar orthorhombic ( $\mathit{Pbca}$) phase to pure antipolar orthorhombic ( $\mathit{Pbca}$) phase at approximately 6.3 GPa. This transformation is irreversible, meaning that upon release, the material is kinetically trapped in the $\mathit{Pbca}$metastable state at 300 K. Compression also drives polar orthorhombic ( $Pca{2}_1$) hafnia into the tetragonal ( $P{4}_2/nmc$) phase, although the latter is not metastable upon release. These results are unified by an analysis of the energy landscape. The fact that pressure allows us to stabilize targeted metastable structures with less Y stabilizer is important to preserving the flat phonon band physics of pure HfO ${}_2$. 

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