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1. Aqueous reactions of organic triplet excited states with atmospheric alkenes

   https://doi.org/10.5194/acp-19-5021-2019  

   Kaur, Richie ; Hudson, Brandi M. ; Draper, Joseph ; Tantillo, Dean J. ; Anastasio, Cort ( January 2019 , Atmospheric Chemistry and Physics)

   Abstract. Triplet excited states of organic matter are formed when colored organicmatter (i.e., brown carbon) absorbs light. While these “triplets” can beimportant photooxidants in atmospheric drops and particles (e.g., theyrapidly oxidize phenols), very little is known about their reactivity towardmany classes of organic compounds in the atmosphere. Here we measure thebimolecular rate constants of the triplet excited state of benzophenone(³BP^∗), a model species, with 17 water-solubleC₃–C₆ alkenes that have either been found in theatmosphere or are reasonable surrogates for identified species. Measured rateconstants ($k_{\mathrm{ALK}+\mathrm{3}{\mathrm{BP}}^{\ast }}$) vary by a factor of 30 and are in therange of (0.24–7.5) ×10⁹ M⁻¹ s⁻¹. Biogenic alkenesfound in the atmosphere – e.g., cis-3-hexen-1-ol, cis-3-hexenyl acetate, andmethyl jasmonate – react rapidly, with rate constants above 1×10⁹ M⁻¹ s⁻¹. Rate constants depend on alkene characteristicssuch as the location of the double bond, stereochemistry, and alkylsubstitution on the double bond. There is a reasonable correlation between$k_{\mathrm{ALK}+\mathrm{3}{\mathrm{BP}}^{\ast }}$ and the calculated one-electron oxidation potential(OP) of the alkenes (R²=0.58); in contrast, rate constants are notcorrelated with bond dissociation enthalpies, bond dissociation freeenergies, or computed energy barriers for hydrogen abstraction. Using the OPrelationship, we estimate aqueous rate constants for a number of unsaturatedisoprene and limonene oxidation products with ³BP^∗: values are inthe range of (0.080–1.7) ×10⁹ M⁻¹ s⁻¹, withgenerally faster values for limonene products. Rate constants with lessreactive triplets, which are probably more environmentally relevant, arelikely roughly 25 times slower. Using our predicted rate constants, alongwith values for other reactions from the literature, we conclude thattriplets are probably minor oxidants for isoprene- and limonene-relatedcompounds in cloudy or foggy atmospheres, except in cases in which the tripletsare very reactive.

    

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2. Patchy Kinetic Sunyaev–Zel’dovich Effect with Controlled Reionization History and Morphology

   https://doi.org/10.3847/1538-4357/ac8481  

   Chen, Nianyi ; Trac, Hy ; Mukherjee, Suvodip ; Cen, Renyue ( February 2023 , The Astrophysical Journal)

   Using the novel semi-numerical code for reionization AMBER, we model the patchy kinetic Sunyaev–Zel’dovich (kSZ) effect by directly specifying the reionization history with the redshift midpointz_mid, duration Δ_z, and asymmetryA_z. We further control the ionizing sources and radiation through the minimum halo massM_hand the radiation mean free pathλ_mfp. AMBER reproduces the free-electron number density and the patchy kSZ power spectrum of radiation–hydrodynamic simulations at the target resolution (1 Mpch⁻¹) with matched reionization parameters. With a suite of (2 Gpc/h)³simulations using AMBER, we first constrain the redshift midpoint 6.0 <z_mid< 8.9 using the Planck 2018 Thomson optical depth result (95% CL). Then, assumingz_mid= 8, we find that the amplitude of$D_{\mathit{\ell }=3000}^{\mathrm{pkSZ}}$scales linearly with the duration of reionization Δ_zand is consistent with the 1σupper limit from South Pole Telescope (SPT) results up to Δ_z< 5.1 (Δ_zencloses 5%–95% ionization). Moreover, a shorterλ_mfpcan lead to a ∼10% lower$D_{\mathit{\ell }=3000}^{\mathrm{pkSZ}}$and a flatter slope in the$D_{\mathit{\ell }=3000}^{\mathrm{pkSZ}}-{\mathrm{\Delta }}_z$scaling relation, thereby affecting the constraints on Δ_zatℓ= 3000. Allowingz_midandλ_mfpto vary simultaneously, we get spectra consistent with the SPT result (95% CL) up to Δ_z= 12.8 (butA_z> 8 is needed to ensure the end of reionization beforez= 5.5). We show that constraints on the asymmetry require ∼0.1μk²measurement accuracy at multipoles other thanℓ= 3000. Finally, we find that the amplitude and shape of the kSZ spectrum are only weakly sensitive toM_hunder a fixed reionization history and radiation mean free path.

    

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3. 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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4. The Direct-method Oxygen Abundance of Typical Dwarf Galaxies at Cosmic High Noon∗

   https://doi.org/10.3847/1538-4357/acb153  

   Gburek, Timothy ; Siana, Brian ; Alavi, Anahita ; Emami, Najmeh ; Richard, Johan ; Freeman, William R. ; Stark, Daniel P. ; Snapp-Kolas, Christopher ( May 2023 , The Astrophysical Journal)

   We present a Keck/MOSFIRE rest-optical composite spectrum of 16 typical gravitationally lensed star-forming dwarf galaxies at 1.7 ≲z≲ 2.6 (z_mean= 2.30), all chosen independent of emission-line strength. These galaxies have a median stellar mass of$\log {(M_{*}/M_{\odot })}_{\mathrm{med}}={8.29}_{-0.43}^{+0.51}$and a median star formation rate of${\mathrm{S}\mathrm{F}\mathrm{R}}_{\mathrm{H}\alpha }^{\mathrm{m}\mathrm{e}\mathrm{d}}={2.25}_{-1.26}^{+2.15}{M}_{\odot }{\mathrm{y}\mathrm{r}}^{-1}$. We measure the faint electron-temperature-sensitive [Oiii]λ4363 emission line at 2.5σ(4.1σ) significance when considering a bootstrapped (statistical-only) uncertainty spectrum. This yields a direct-method oxygen abundance of$12+\log {(\mathrm{O}/\mathrm{H})}_{\mathrm{direct}}={7.88}_{-0.22}^{+0.25}$(${0.15}_{-0.06}^{+0.12}{Z}_{\odot }$). We investigate the applicability at highzof locally calibrated oxygen-based strong-line metallicity relations, finding that the local reference calibrations of Bian et al. best reproduce (≲0.12 dex) our composite metallicity at fixed strong-line ratio. At fixedM_*, our composite is well represented by thez∼ 2.3 direct-method stellar mass—gas-phase metallicity relation (MZR) of Sanders et al. When comparing to predicted MZRs from the IllustrisTNG and FIRE simulations, having recalculated our stellar masses with more realistic nonparametric star formation histories$(\log {(M_{*}/M_{\odot })}_{\mathrm{med}}={8.92}_{-0.22}^{+0.31})$, we find excellent agreement with the FIRE MZR. Our composite is consistent with no metallicity evolution, at fixedM_*and SFR, of the locally defined fundamental metallicity relation. We measure the doublet ratio [Oii]λ3729/[Oii]λ3726 = 1.56 ± 0.32 (1.51 ± 0.12) and a corresponding electron density of$n_e=1_{-0}^{+215}{\mathrm{cm}}^{-3}$($n_e=1_{-0}^{+74}{\mathrm{cm}}^{-3}$) when considering the bootstrapped (statistical-only) error spectrum. This result suggests that lower-mass galaxies have lower densities than higher-mass galaxies atz∼ 2.

    

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5. Validation of Elemental and Isotopic Abundances in Late-M Spectral Types with the Benchmark HIP 55507 AB System

   https://doi.org/10.3847/1538-4357/ad1243  

   Xuan, Jerry W. ; Wang, Jason ; Finnerty, Luke ; Horstman, Katelyn ; Grimm, Simon ; Peck, Anne E. ; Nielsen, Eric ; Knutson, Heather A. ; Mawet, Dimitri ; Isaacson, Howard ; et al ( February 2024 , The Astrophysical Journal)

   M dwarfs are common host stars to exoplanets but often lack atmospheric abundance measurements. Late-M dwarfs are also good analogs to the youngest substellar companions, which share similarT_eff∼ 2300–2800 K. We present atmospheric analyses for the M7.5 companion HIP 55507 B and its K6V primary star with Keck/KPIC high-resolution (R∼ 35,000)K-band spectroscopy. First, by including KPIC relative radial velocities between the primary and secondary in the orbit fit, we improve the dynamical mass precision by 60% and find$M_B={88.0}_{-3.2}^{+3.4}{M}_{\mathrm{Jup}}$, putting HIP 55507 B above the stellar–substellar boundary. We also find that HIP 55507 B orbits its K6V primary star with$a={38}_{-3}^{+4}$au ande= 0.40 ± 0.04. From atmospheric retrievals of HIP 55507 B, we measure [C/H] = 0.24 ± 0.13, [O/H] = 0.15 ± 0.13, and C/O = 0.67 ± 0.04. Moreover, we strongly detect¹³CO (7.8σsignificance) and tentatively detect${\mathrm{H}}_2^{18}\mathrm{O}$(3.7σsignificance) in the companion’s atmosphere and measure${}^{12}\mathrm{CO}{/}^{13}\mathrm{CO}={98}_{-22}^{+28}$and${\mathrm{H}}_2^{16}\mathrm{O}/{\mathrm{H}}_2^{18}\mathrm{O}={240}_{-80}^{+145}$after accounting for systematic errors. From a simplified retrieval analysis of HIP 55507 A, we measure${}^{12}\mathrm{CO}{/}^{13}\mathrm{CO}={79}_{-16}^{+21}$and${\mathrm{C}}^{16}\mathrm{O}/{\mathrm{C}}^{18}\mathrm{O}={288}_{-70}^{+125}$for the primary star. These results demonstrate that HIP 55507 A and B have consistent¹²C/¹³C and¹⁶O/¹⁸O to the <1σlevel, as expected for a chemically homogeneous binary system. Given the similar flux ratios and separations between HIP 55507 AB and systems with young substellar companions, our results open the door to systematically measuring¹³CO and${\mathrm{H}}_2^{18}\mathrm{O}$abundances in the atmospheres of substellar or even planetary-mass companions with similar spectral types.

    

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