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46 records · Page 3

Directed Gas-Phase Formation of Azulene (C 10 H 8 ): Unraveling the Bottom-Up Chemistry of Saddle-Shaped Aromatics

The azulene (C 10 H 8 ) molecule, the simplest polycyclic aromatic hydrocarbon (PAH) carrying a fused seven- and five-membered ring, is regarded as a fundamental molecular building block of saddle-shaped carbonaceous nanostructures such as curved nanographenes in the interstellar medium. However, an understanding of the underlying gas-phase formation mechanisms of this nonbenzenoid 10π-Hückel aromatic molecule under low-temperature conditions is in its infancy. Here, by merging crossed molecular beam experiments with electronic structure calculations and molecular dynamics simulations, our investigations unravel an unconventional low-temperature, barrierless route to azulene via the reaction of the simplest organic radical, methylidyne (CH), with indene (C 9 H 8 ) through ring expansion. This reaction might represent the initial step toward to the formation of saddle-shaped PAHs with seven-membered ring moieties in hydrocarbon-rich cold molecular clouds such as the Taurus Molecular Cloud-1 (TMC-1). These findings challenge conventional wisdom that molecular mass growth processes to nonplanar PAHs, especially those containing seven-membered rings, operate only at elevated pressure and high-temperature conditions, thus affording a versatile low-temperature route to contorted aromatics in our galaxy.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Dimensionless parameters for cloudy Rayleigh-Bénard convection: Supersaturation, Damköhler, and Nusselt numbers

In steady-state Rayleigh-Bénard convection, heat is transported by turbulent thermal convection from the bottom, hot surface to the top, cold surface, leading to a height-independent sensible heat flux. When water vapor is present and cloud formation occurs, there is also an additional latent heat flux. Heat transport in cloudy Rayleigh-Bénard convection depends on turbulent flow as well as the microphysical state of the clouds: specifically, whether substantial supersaturations exist and whether cloud liquid water is removed through sedimentation/precipitation. In this article we bridge between the Rayleigh-Bénard convection literature and the atmospheric literature. We express the governing equations for cloudy convection in dimensionless form, thereby explicitly identifying the governing parameters relevant to the cloudy case, including Schmidt, Damköhler, supersaturation, and sedimentation numbers. We further connect to the atmospheric literature by obtaining a Nusselt number (dimensionless heat flux) for a cloud-convection system, directly from the conservation equations for temperature and water vapor. This flux has the same form as that identified by Zhang et al. [L. Zhang, K. L. Chong, and K.-Q. Xia, J. Fluid Mech. 874, 1041 (2019)] for convection with water vapor, but is extended to the cloudy case. For equal thermal and water vapor diffusivities, the flux corresponds to the widely used atmospheric quantities equivalent temperature and moist static energy. Using large eddy simulation (LES) of an idealized cloudy Rayleigh-Bénard convection system with fixed boundary conditions, we find that the equivalent heat flux (Nusselt number) is only weakly dependent on the microphysical details of the system, such as liquid water mixing ratio and cloud droplet number concentration. Finally, from the results, we show the vertical profiles of sensible and latent heat fluxes depend on the liquid water content, whereas the equivalent heat flux remains a constant throughout the height of the chamber.

54 ENVIRONMENTAL SCIENCES↗

Clouds, hazes, and the stratospheric methane abundance in Neptune

Analysis of high-spatial-resolution (approximately 0.8 arcsec) methane band and continuum imagery of Neptune's relatively homogeneous Equatorial Region yields significant constraints on (1) the stratospheric gaseous methane mixing ratio (f(sub CH4, S)), (2) the column abundances and optical properties of stratospheric and tropospheric hydrocarbon hazes, and (3) the wavelength-dependent single-scattering albedo of the 3-bar opaque cloud. From the center-to-limb behavior of the 7270-A and 8900-A CH4 bands, the stratospheric methane mixing ratios is limited to f(sub CH4, S) less than 1.7 x 10(exp -3), with a nominal value of f(sub CH4, S) = 3.5 x 10(exp -4), one to two orders of magnitude less than pre-Voyager estimates, but in agreement with a number of recent ultraviolet and thermal infrared measurements, and largely in agreement with the tropopause mixing ratio implied by Voyager temperature measurements. Upper limits to the stratospheric haze mass column abundance and 6190-A and 8900-A haze opacities are 0.61 micrograms/sq cm and 0.075 and 0.042, respectively, with nominal values of 0.20 micrograms/sq cm and 0.025 and 0.014 for the 0.2 micrometers radius particles preferred by the recent Voyager PPS analysis of Pryor et al. (1992). The tropospheric CH4 haze opacities are comparable to that found in the stratosphere, i.e., upper limits of 0.104 and 0.065 at 6190 A and 8900 A, respectively, with nominal values of 0.085 and 0.058. This indicates a column abundance less than 11.0 micrograms/sq cm, corresponding to the methane gas content within a well-mixed 3% methane tropospheric layer only 0.1 cm thick near the 1.5-bar CH4 condensation level. Conservative scattering is ruled out for the opaque cloud near 3 bars marking the bottom of the visible atmosphere. Specifically, we find cloud single-scattering albedos of 0.915 +/- 0.006 at 6340 A, 0.775 +/- 0.012 at 7490 A, and 0.803 +/- 0.010 at 8260 A. Global models utilizing a complete global spectrum confirm the red-absorbing character of the 3-bar cloud. The global-mean model has approximately 7.7 times greater stratospheric aerosol content than the Equatorial Region. An analysis of stratospheric haze precipitation rates indicates a steady-state haze production rate of 0.185-1.5 x 10(exp -14) g/sq cm/s, in agreement with recent theoretical photochemical estimates. Finally, reanalysis of the Voyager PPS 7500-A phase angle data utilizing the f(sub CH4, S) value derived here confirms the Pryor et al. result of a tropospheric CH4 haze opacity of a few tenths in the 22-30 degs S latitude region, several times that of the Equatorial Region or of the globe. The factor-of-10 reduction in f(sub CH4, S) below that assumed by Pryor et al. implies decreased gas absorption and consequently a decrease in the forward-scattering component of tropospheric aerosols.

Baines, Kevin H.↗

Aerosol Midlatitude Cyclone Indirect Effects in Observations and High-Resolution Simulations

Aerosol-cloud interactions are a major source of uncertainty in inferring the climate sensitivity from the observational record of temperature. The adjustment of clouds to aerosol is a poorly constrained aspect of these aerosol-cloud interactions. Here, we examine the response of midlatitude cyclone cloud properties to a change in cloud droplet number concentration (CDNC). Idealized experiments in high-resolution, convection-permitting global aquaplanet simulations with constant CDNC are compared to 13 years of remote-sensing observations. Observations and idealized aquaplanet simulations agree that increased warm conveyor belt (WCB) moisture flux into cyclones is consistent with higher cyclone liquid water path (CLWP). When CDNC is increased a larger LWP is needed to give the same rain rate. The LWP adjusts to allow the rain rate to be equal to the moisture flux into the cyclone along the WCB. This results in an increased CLWP for higher CDNC at a fixed WCB moisture flux in both observations and simulations. If observed cyclones in the top and bottom tercile of CDNC are contrasted it is found that they have not only higher CLWP but also cloud cover and albedo. The difference in cyclone albedo between the cyclones in the top and bottom third of CDNC is observed by CERES to be between 0.018 and 0.032, which is consistent with a 4.6-8.3 Wm(exp -2) in-cyclone enhancement in upwelling shortwave when scaled by annual-mean insolation. Based on a regression model to observed cyclone properties, roughly 60% of the observed variability in CLWP can be explained by CDNC and WCB moisture flux.

Mccoy, Daniel T.↗

Satellite-Based Surface Heat Budgets and Sea Surface Temperature Tendency in the Tropical Eastern Indian and Western Pacific Oceans for the 1997/98 El Nino and 1998/99 La Nina

The 1997/98 is a strong El Nino warm event, while the 1998/99 is a moderate La Nina cold event. We have investigated surface heat budgets and sea surface temperature (SST) tendency for these two events in the tropical western Pacific and eastern Indian Oceans using satellite-retrieved surface radiative and turbulent fluxes. The radiative fluxes are taken from the Goddard Satellite-retrieved Surface Radiation Budget (GSSRB), derived from radiance measurements of the Japanese Geostationary Meteorological Satellite 5. The GSSRB covers the domain 40 deg S - 4 deg N, 90 deg E-17 deg W and a period from October 1997 to December 2000. The spatial resolution is 0.5 deg x 0.5 deg lat-long and the temporal resolution is 1 day. The turbulent fluxes are taken from Version 2 of the Goddard Satellite-based Surface Turbulent Fluxes (GSSTF-2). The GSSTF-2 has a spatial resolution of 1 deg x 1 deg lat-long over global Oceans and a temporal resolution of 1 day covering the period July 1987-December 2000. Daily turbulent fluxes are derived from the S S M (Special Sensor Microwave/Imager) surface wind and surface air humidity, and the SST and 2-m air temperature of the NCEP/NCAR reanalysis, using a stability-dependent bulk flux algorithm. The changes of surface heat budgets, SST and tendency, cloudiness, wind speed, and zonal wind stress of the 1997/98 El Nino relative to the1998/99 La Nina for the northern winter and spring seasons are analyzed. The relative changes of surface heat budgets and SST tendency of the two events are quite different between the tropical eastern Indian and western Pacific Oceans. For the tropical western Pacific, reduced solar heating (more clouds) is generally associated with decreased evaporative cooling (weaker winds), and vise versa. The changes in evaporative cooling over-compensate that of solar heating and dominate the spatial variability of the changes in net surface heating. Both solar heating and evaporative cooling offset each other to reduce interannual variability of net surface heating. In addition, the area of increased SST tendency is larger than that of increased net surface heating, due to less solar radiation penetration through the bottom of deeper ocean mixed layer (stronger winds). For the tropical eastern Indian Ocean, enhanced solar heating (less clouds) is generally associated with reduced evaporative cooling (weaker winds). Both solar heating and evaporative cooling reinforce each other to increase interannual variability of net surface heating. In addition, the area of increased SST tendency is smaller than that of increased net surface heating in the southern domain. The relative changes in wind and zonal wind stress indicate more solar radiation penetration through the ocean mixed layer and more northward heat transport by Ocean current from the south to the north Indian Ocean for the El Nino than for the La Nina.

Chou, Shu-Hsien↗

Characterization of Individual Aerosol Particles Associated with Clouds (CRYSTAL-FACE)

The aim of our research was to obtain data on the chemical and physical properties of individual aerosol particles from near the bottoms and tops of the deep convective systems that lead to the generation of tropical cirrus clouds and to provide insights into the particles that serve as CCN or IN. We used analytical transmission electron microscopy (ATEM), including energy-dispersive X-ray spectrometry (EDS) and electron energy-loss spectroscopy (EELS), and field-emission electron microscopy (FESEM) to compare the compositions, concentrations, size distributions, shapes, surface coatings, and degrees of aggregation of individual particles from cloud bases and the anvils near the tropopause. Aggregates of sea salt and mineral dust, ammonium sulfate, and soot particles are abundant in in-cloud samples. Cirrus samples contain many H2SO4 droplets, but acidic sulfate particles are rare at the cloud bases. H2SO4 probably formed at higher altitudes through oxidation of SO2 in cloud droplets. The relatively high extent of ammoniation in the upper troposphere in-cloud samples appears to have resulted from vertical transport by strong convection. The morphology of H2SO4 droplets indicates that they had been at least yartiy ammoniated at the time of collection. They are internally mixed with organic materials, metal sulfates, and solid particles of various compositions. Ammoniation and internal mixing of result in freezing at higher temperature than in pure H2SO4 aerosols. K- and S-bearing organic particles and Si-Al-rich particles are common throughout. Sea salt and mineral dust were incorporated into the convective systems from the cloud bases and worked as ice nuclei while being vertically transported. The nonsulfate particles originated from the lower troposphere and were transported to the upper troposphere and lower stratosphere.

Buseck, Peter R.↗

Global Gravity Wave Variances from Aura MLS: Characteristics and Interpretation

The gravity wave (GW)-resolving capabilities of 118-GHz saturated thermal radiances acquired throughout the stratosphere by the Microwave Limb Sounder (MLS) on the Aura satellite are investigated and initial results presented. Because the saturated (optically thick) radiances resolve GW perturbations from a given altitude at different horizontal locations, variances are evaluated at 12 pressure altitudes between 21 and 51 km using the 40 saturated radiances found at the bottom of each limb scan. Forward modeling simulations show that these variances are controlled mostly by GWs with vertical wavelengths z 5 km and horizontal along-track wavelengths of y 100-200 km. The tilted cigar-shaped three-dimensional weighting functions yield highly selective responses to GWs of high intrinsic frequency that propagate toward the instrument. The latter property is used to infer the net meridional component of GW propagation by differencing the variances acquired from ascending (A) and descending (D) orbits. Because of improved vertical resolution and sensitivity, Aura MLS GW variances are 5?8 times larger than those from the Upper Atmosphere Research Satellite (UARS) MLS. Like UARS MLS variances, monthly-mean Aura MLS variances in January and July 2005 are enhanced when local background wind speeds are large, due largely to GW visibility effects. Zonal asymmetries in variance maps reveal enhanced GW activity at high latitudes due to forcing by flow over major mountain ranges and at tropical and subtropical latitudes due to enhanced deep convective generation as inferred from contemporaneous MLS cloud-ice data. At 21-28-km altitude (heights not measured by the UARS MLS), GW variance in the tropics is systematically enhanced and shows clear variations with the phase of the quasi-biennial oscillation, in general agreement with GW temperature variances derived from radiosonde, rocketsonde, and limb-scan vertical profiles.

MLS (MICROWAVE LIMB SOUNDER)↗

Chemical Recycling of Polycaprolactones via Reactive Melt Processing

Chemical recycling is a promising technology for the deconstruction of waste plastics into monomers or other chemical intermediates, which can be converted into other value-added products or repolymerized into polymers. In this work, polycaprolactone and poly(4-propylcaprolactone) were chemically recycled by exploiting ring-closing depolymerization (RCD). To demonstrate the utility of this approach, reactive distillation experiments were initially conducted in a heated round-bottom flask with a distillation head to explore the effect of temperature and catalyst loading on RCD. Inspired by industrial devolatilization equipment, analogous experiments were conducted using a twin-screw melt compounder that was modified to simultaneously heat and mix polymer in the presence of a catalyst while continuously removing the evolved monomer vapors with a vacuum system and collecting them in a cold trap. Yield and selectivity of the recovered monomer were characterized by 1 H nuclear magnetic resonance spectroscopy and gas chromatography-mass spectrometry. Importantly, the more scalable twin-screw melt compounder approach produced values of monomer selectivity (∼90%) and yield (∼80%) similar to those of the round-bottom flask experiments. The recovered monomers were also successfully repolymerized into the same neat polymer with comparable molar masses without purification steps or adding initiator. Here, the results of this study promote the use of reactive devolatilization extrusion as a scalable approach to polyester depolymerization.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Interaction Between Surface Heat Budgets, Sea Surface Temperature and Deep Convection in the Tropical Western Pacific

The surface heat budgets, sea surface temperature (SST), clouds and winds in the tropical western Pacific are analyzed and compared for the periods April-June 1998 and 1999. The spring of 1998 is in the later phase of a strong El Nino, whereas the spring of 1999 is in a period of a La Nina. The surface shortwave (SW) and longwave (LW) radiative fluxes are retrieved from Japanese Geostationary Meteorological Satellite radiance measurements, while the surface turbulent fluxes (latent and sensible heat) are derived from SSM/I-Inferred surface air humidity and winds. The SST and sea-air temperature differences are taken from NCEP/NCAR reanalysis. Deep convection is inferred from the outgoing longwave radiation of NOAA's polar-orbiting satellites. The longitudinal shift in maximum SST, deep convection and winds during El Nino and La Nina have a large impact on the spatial distribution of surface heating. Changes in clouds between these two periods have a large impact on the monthly-mean radiative heating, exceeding 60 W m(exp -2) over large oceanic regions. Similarly, the differences in wind speeds and SST have a large impact on the latent cooling, exceeding 40 W m(exp -2) over large oceanic areas. However, the maximum impacts on radiative and latent heat fluxes occur in different regions. The regions of maximum impact on radiative fluxes coincide with the regions of maximum change in clouds, whereas regions of maximum impact on turbulent heat fluxes coincide with the regions of maximum change in trade winds. The time-evolution of SST in relation to that of surface heat fluxes and winds are investigated and compared between the two El Nino and La Nina periods. In regions where wind speeds (or wind stresses) are large, the change in SST agrees well with the change in the net surface heating, indicating a deep ocean mixed layer associated with strong trade winds. On the other hand, in regions where radiative fluxes are large, the change in SST does not agree well with the change in the net surface heating, indicating the importance of solar radiation penetrating through the bottom of the shadow ocean mixed layer.

Chou, Shu-Hsien↗

Surface Biology and Geology (SBG) Thermal Infrared (TIR) Free -Flyer Concept

Scientists and engineers from the United States and Italy are developing a thermal infrared (TIR) free-flyer concept that forms an essential element of the NASA Surface Biology & Geology (SBG) designated observable and the greater NASA Earth System Observatory (ESO), which also includes observations of aerosols, clouds, convection, and precipitation; mass change; and surface deformation & change.In response to the recommendations from the 2017 National Academies decadal survey for Earth science, NASA initiated the SBG designated observable with five key research and applications focus areas: ecosystems and natural resources, hydrology, weather, climate, and solid Earth. SBG includes spaceborne measurements of hyperspectral imagery in the visible to shortwave infrared (0.4-2.5 um) and multispectral imagery in the mid and thermal infrared (3-12 um) that provide the remote sensing data needed to inform each research and applications area. High-level TIR data products include Earth surface temperature & emissivity, evapotranspiration, substrate composition, volcanic plumes, and high-temperature features. While the science, applications, and technology build on prior mission studies conducted for more than a decade, it has only been recently that a joint team of scientists and engineers from the NASA Jet Propulsion Laboratory (JPL), Agenzia Spaziale Italiana (ASI), Istituto Nazionale Geofisica e Volcanologia (INGV), and the Istituto Nazionale Astrofisica (INAF) have developed a compelling concept for a TIR free-flyer. In this concept, the TIR instrument is an eight-band radiometer. Seven of the bands are between 3 and 12 um with an additional band at 1.65 um. The instrument’s 68.8 deg total viewing angle and the free-flyer’s 665 km operational altitude results in a ground sampling distance (GSD) of <60 m at nadir, produces a swath width of 935 km, and allows for a 2-3-day revisit time. A two-band visible and near infrared (VNIR) camera, with <30 m GSD at nadir and 935 km swath width, will complement the TIR instrument. VNIR high-level data products include top & bottom of atmosphere reflectance and normalized difference vegetation indices (NDVI). The TIR instrument and VNIR camera will be mounted on a PLATiNO+ spacecraft, a multi-application, reconfigurable, and scalable platform. The launcher selected for the TIR free-flyer is the VEGA-C. To maximize the science and applications benefits the SBG-TIR free-flyer team are collaborating with personnel from the ESA Land Surface Temperature Monitoring mission (LSTM) as well individuals from the Thermal Infrared Imaging Satellite for High-resolution Natural resource Assessment (TRISHNA), a joint mission by CNES and ISRO. Pre-Phase A concept studies for the SBG-TIR free-flyer commenced in the spring 2021. This allows for the concept to be refined; for technical risks to be identified and mitigated, as necessary; and strategies for reducing the development schedule to be defined and assessed before conducting a NASA-ASI Mission Concept Review (MCR) in the spring of 2022 and a NASA Key Decision Point-A (KDP-A) as early as the summer of 2022. These are key milestones in being able to launch and begin operating the SBG-TIR free-flyer in the second half of the decade, so that many of the questions posed by the National Academies in the 2017 decadal survey can be answered.

Fabrizia-Buongiorno, Maria↗