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At least 595 records · Page 33

Can Silicon-Smelting Contribute to the Low O/Si Ratio on the Surface of Mercury?

The MErcury Surface, Space ENvironment, GEochemistry, and Ranging (MESSENGER) spacecraft collected data that provided important insights into the structure, chemical makeup, and compositional diversity of Mercury. Among the many discoveries about Mercury made by MESSENGER, several surprising compositional characteristics of the surface were observed. These discoveries include elevated sulfur abundances (up to 4 wt.%), elevated abundances of graphitic carbon (0-4.1 wt.% across the surface with an additional 1-3 wt.% graphite above the global average in low reflectance materials), low iron abundances (less than 2 wt.%), and low oxygen abundances (O/Si weight ratio of 1.20+/-0.1). These exotic characteristics likely have important implications for the thermochemical evolution of Mercury and point to a planet that formed under highly reducing conditions. In the present study, we focus specifically on the low O/Si ratio of Mercury, which is anomalous compared to all other planetary materials. A recent study that considered the geochemical implications of the low O/Si ratio reported that 12-20% of the surface materials on Mercury are composed of Si-rich, Si-Fe alloys. They further postulated that the origin of the metal is best explained by a combination of space weathering and graphite-induced smelting that was facilitated by interaction of graphite with boninitic and komatiitic parental liquids. The goal of the present study is to assess the plausibility of smelting on Mercury through experiments run at the conditions that McCubbin et al. indicated would be favorable for Si-smelting.

McCubbin, F. M.↗

The Role of Carbon in Exotic Crust Formation on Mercury

The terrestrial planets that comprise our inner Solar System, including the Moon, are all rocky bodies that have differentiated into a crust, mantle, and core. Furthermore, all of these bodies have undergone various igneous processes since their time of primary crust formation. These processes have resurfaced each of these bodies, at least in part, resulting in the production of a secondary crust, to which Mercury is no exception. From its first flyby encounter with Mercury on January 14, 2008, the MErcury Surface, Space ENvironment, GEochemistry and Ranging (MESSENGER) spacecraft collected data on the structure, chemical makeup, and density of the planet among other important characteristics. The X-Ray Spectrometer on board MESSENGER measured elevated abundances of sulfur and low abundances of iron, suggesting the planets oxygen fugacity (fO2) is several log10 units below the Iron-Wustite buffer. Similar to the role of other volatiles (e.g. sulfur) on highly reducing planetary bodies, carbon is expected to behave differently in an oxygen starved environment than it does in an oxygen enriched environment (e.g., Earth).

Vander Kaaden, Kathleen E.↗

The Exoplanet Climate Infrared TElescope (EXCITE)

Although there are a large number of known exoplanets, there is little data on their global atmospheric properties.Phase-resolved spectroscopy of transiting planets - continuous spectroscopic observation of planets during their full orbits - probes varied depths and longitudes in the atmospheres thus measuring their three-dimensional thermal and chemical structure and contributing to our understanding of their global circulation. Planets with characteristics suitable for atmospheric characterization have orbits of several days, so phase curve observations are highly resource intensive, especially for shared use facilities. The Exoplanet Climate Infrared TElescope (EXCITE) is a balloon-borne near-infrared spectrometer designed to observe from 1 to 5 meters to perform phase-resolved spectroscopy of hot Jupiters. Flying from a long duration balloon (LDB) platform, EXCITE will have the stability to continuously stare at targets for days at a time and the sensitivity to produce data of the quality and quantity needed to signicantly advance our understanding of exoplanet atmospheres. We describe the EXCITE design and show results of analytic and numerical calculations of the instrument sensitivity. We show that an instrument like EXCITE will produce a wealth of quality data, both complementing and serving as a critical bridge between current and future space-based near infrared spectroscopic instruments.

Spectroscopy↗

Corrosion Behavior of Stainless Steel 304 and Nickel 625 Under Iodine Vapor at 300 °C

The chemical, structural, and microstructural behavior of stainless steel 304 (SS 304) and nickel 625 (Ni 625) were probed after exposure to iodine vapor laminar flow at 300 °C. This work was conducted in support of the development of in-space propulsion utilizing iodine as a propellant. The kinetics of corrosion was measured in a custom-built iodine-compatible thermogravimetric analyzer rig at 300 °C in which samples were exposed to an iodine laminar vapor flow of 1 mg/min (carried by 20 mL/min argon gas) for up to 31 days. Samples were characterized after the experiment by X-ray diffraction, electron microscopy, energy dispersive X-ray spectroscopy, and dynamic secondary ion mass spectrometry. All samples formed scales consisting mainly of metal oxyiodides showing different chemistry, microstructure, and crystalline phases. The paralinear rate law best describes the kinetics of oxidation of the samples. SS 304 exhibited slightly slower kinetics of oxidation (106±3·10(exp –5) mg/sq.cm/day) than Ni 625 (122±3·10(exp –5) mg/sq.cm/day) in the low-oxygen and low-water environment.

Chemistry and Materials↗

James Clerk Maxwell Telescope Spectral and Continuum Imaging of Hyperactive Comet 46P/Wirtanen

The Jupiter-family comet (JFC) 46P/Wirtanen passed the Earth at a distance of 0.077 au on 2018 December 16 UT, presenting a rare opportunity to study the chemical structure of its coma. With the James Clerk Maxwell Telescope we achieved a resolution of 800 km, which is smaller than the scale lengths of some distributed cometary molecules at the comet's heliocentric distance of 1 au. Spectroscopic observations of the J = 4 − 3 transition of HCN showed generally uniform levels of outgassing activity during the observing period, 2018 December 14–20. Gas expansion velocities were ~0.6 km s−1, and the derived average HCN production rate was 7.4 × 1024 mol s−1. HCN and CH3OH emissions were detected at least 30'' (1600 km) from the nucleus, and the abundances of these species were typical for a JFC. The radial distribution of CH3OH is consistent with an extended source of sublimation such as a population of icy grains—cometary halo ice primaries, or CHIPs—as has been invoked previously to explain hyperactivity in comets. The abundance of H2CO is normal if it is a daughter species. HNC and CO were not detected, but a sensitive nondetection of CS implies an unusually low CS:H2O ratio of <0.02%. The peak brightness of the 850 μm continuum emissions from icy coma dust particles of size ~1 mm fell from (52 ± 6) to (40 ± 3) mJy beam−1 through the week, while the size of the dust coma remained essentially constant, with dust extending to ~1000 km from the nucleus. The total mass of those particles was ~2 × 108 kg.

Ian M Coulson↗

High Energy Dynamic Impact Testing of APC AS4D/PEKK-FC and TC1225 LMPAEK T700G Thermoplastic Composite Materials

High energy dynamic impact tests were conducted on AS4/PEKK and TC1225 LMPAEK T700G thermoplastic quasi-isotropic laminated tape composite panels. The primary objective was to provide data for evaluation of computational composite impact models. Measurements include transient deformations, pre- and post-test characterization of delamination and energy threshold for onset of delamination and onset of penetration. Empirical results indicate an approximately 50% increase in penetration threshold velocity and over 100% increase in penetration energy threshold for the TC1225 LMPAEK T700G composite compared to the AS4/PEKK composite. The velocity required to produce NDE-detectable delamination in the TC1225 LMPAEK T700G composite was roughly twice that for the AS4/PEKK composite. Results will be compared with those from a thermoset composite system with a similar architecture. Because of differences in the chemical structure of the two resins, differences in the impact response are to be expected.

Impact↗

A Multimodel Investigation of Asian Summer Monsoon UTLS Transport Over the Western Pacific

The Asian summer monsoon (ASM) as a chemical transport system is investigated using a suite of models in preparation for an airborne field campaign over the Western Pacific. Results show that the dynamical process of anticyclone eddy shedding in the upper troposphere rapidly transports convectively uplifted Asian boundary layer air masses to the upper troposphere and lower stratosphere over the Western Pacific. The models show that the transported air masses contain significantly enhanced aerosol loading and a complex chemical mixture of trace gases that are relevant to ozone chemistry. The chemical forecast models consistently predict the occurrence of the shedding events, but the predicted concentrations of transported trace gases and aerosols often differ between models. The airborne measurements to be obtained in the field campaign are expected to help reduce the model uncertainties. Furthermore, the large-scale seasonal chemical structure of the monsoon system is obtained from modeled carbon monoxide, a tracer of the convective transport of pollutants, which provides a new perspective of the ASM circulation, complementing the dynamical characterization of the monsoon.

Laura L. Pan↗

Microbial Pigments and Their Degradation Products as Biosignatures

Carotenoids are a class of vibrant biological pigments that have a characteristic chemical structure centered around a polyene core (Lu et al. 2018). Carotenoids and their derivatives are candidate biosignatures because they can persist in the terrestrial geologic record for up to 1.73 billion years (Vinnichenko et al. 2020), have specific structures that are likely the result of complex pathways, mediate the survival of many microorganisms in Mars and Ocean Worlds analog environments, and are detectable with multiple techniques, including Raman spectroscopy. In this project, we aim to investigate the detectability of carotenoid pigments with different spectroscopic methods to inform future instrument selection. We compare the spectra of five unaltered carotenoids, two model compounds, and carotenoid-forming archaeon with visible and deep UV Raman spectroscopy and UVVis absorption spectrophotometry. We then use one model pigment, beta-carotene, to evaluate the likelihood that unique spectral properties of carotenoids, or their refractory byproducts, would be preserved and detectable on a remote planetary surface by exposing it to simulated conditions for Mars. Sample Acquisition. Pigments betacarotene, lutein, zeaxanthin, astaxanthin, and lycopene were purchased from Sigma Aldrich. Halobacterium salinarum NRC-1 was acquired from Carlina Biological and grown in Halobacterium media. Mineral salts including sodium sulfate, sodium carbonate, and halite were used to form matrices in which the beta-carotene was embedded before exposure. Pigment-mineral mixes were at a 1:10 ratio in water. Analytical Techniques. Deep UV Raman data were collected on a custom laboratory mapping spectrometer called MOBIUS (Mineral and Organic Based Investigations using Ultraviolet Spectroscopy), which is an analog to the SHERLOC instrument on the Mars 2020 Perseverance rover (Bhartia et al. 2021). It features a 248.56 nm NeCu pulsed laser, liquid nitrogen-cooled detector, and tunable optical setup. Visible Raman data were collected using a Horiba Jobin Yvon LabRam HR spectrometer with a frequencydoubled Nd:YAG laser (532 nm) and a HeNe laser (633 nm). A VWR 6300 PC UV/Visible Spectrophotometer was used to collect absorption data for carotenoid solutions, model compounds, and solvents in UVpermissible capped cuvettes. Data were collected from 190-1100 nm at 1 nm increments. All spectral data were analyzed using Igor Pro 9 (Wavemetrics). Irradiation. We used a vacuum chamber equipped with a cryostat and a flood electron gun to simulate Martian surface temperatures, low pressures, and ionizing radiation (10keV, 10μA for 6h at 200K for our initial tests). The samples were prepared by drying the pigment-mineral mix onto polished metal tabs, then mounted on the cryostat for processing. Samples were then analyzed directly on the tabs after exposure. Results: In comparing the visible and deep UV Raman spectra of unaltered pigments, we found that they differed drastically. Carotenoids are often studied with visible Raman and typically have peaks at 1525 cm-1 and 1157 cm-1, due to the stretching of the C=C and C-C bonds in the polyene structure. However, in deep UV, the strongest feature is at ~1630 cm-1 and is broad, possibly indicating that multiple peaks are forming this feature. This stark difference is likely due to different preresonant enhancement effects. The UV-Vis results show that there is an absorption band in the deep UV <300 nm, which supports the hypothesis that the 248.6 nm excitation is interrogating another aspect of carotenoids than visible Raman. Our preliminary exposure tests indicated that pigments – even without minerals present - were largely unaltered in the applied conditions, with only a slight broadening in the primary polyene peaks apparent in the visible Raman data. Figure 1. A) Visible vs. deep UV Raman spectra of unaltered beta carotene. B) Schematic of exposure. Conclusions: Our results to date indicate that deep UV and visible Raman spectroscopy, both techniques with planetary mission heritage from Mars 2020 (Wiens et al. 2021, Bhartia et al. 2021), may be used in a complementary manner to observe carotenoids. In addition, we find that beta-carotene is largely resistant to our current exposure conditions, though there may be some amount of amorphization of the material which could cause the broadening of the peaks at 1525 and 1157 cm-1. As a next step, we aim to increase the dosage and duration of exposure to observe degradation of the parent pigment, possibly add UV as a factor via an Ar mini-arc UV lamp and use GC-MS to characterize possible degradation products.

pigments↗

Hydrophilic, light active coating for membranes

A porous membrane provides enhanced filtration of pollutants and particles by coating the membrane with conformal thin films of doped titanium dioxide via atomic layer deposition or, alternatively, sequential infiltration synthesis. The membrane can either be organic or inorganic, and the doping of the membrane, usually with nitrogen, is an important feature that shifts the optical absorption of the TiO2 from the UV range into the visible-light range. This enables the use of lower energy light, including sunlight, to activate the photocatalytic function of the film. The coating described in the present invention is compatible with virtually any porous membrane and allows for precise tuning of the pore size with molecular precision. The present invention presents a new coating process and chemical structure that provides catalytic activity, strongly enhanced by light, to both mitigate fouling and break down various organic pollutants in the process stream.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Modeling of Hidden Structures Using Sparse Chemical Shift Data from NMR Relaxation Dispersion

NMR relaxation dispersion measurements report on conformational changes occurring on the μs-ms timescale. Chemical shift information derived from relaxation dispersion can be used to generate structural models of weakly populated alternative conformational states. Current methods to obtain such models rely on determining the signs of chemical shift changes between the conformational states, which are difficult to obtain in many situations. Here, we use a “sample and select” method to generate relevant structural models of alternative conformations of the C-terminal-associated region of Escherichia coli dihydrofolate reductase (DHFR), using only unsigned chemical shift changes for backbone amides and carbonyls ( 1 H, 15 N, and 13 C'). We find that CS-Rosetta sampling with unsigned chemical shift changes generates a diversity of structures that are sufficient to characterize a minor conformational state of the C-terminal region of DHFR. The excited state differs from the ground state by a change in secondary structure, consistent with previous predictions from chemical shift hypersurfaces and validated by the x-ray structure of a partially humanized mutant of E. coli DHFR (N23PP/G51PEKN). The results demonstrate that the combination of fragment modeling with sparse chemical shift data can determine the structure of an alternative conformation of DHFR sampled on the μs-ms timescale. Such methods will be useful for characterizing alternative states, which can potentially be used for in silico drug screening, as well as contributing to understanding the role of minor states in biology and molecular evolution.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Impact of n -Butylammonium Bromide on the Chemical and Electronic Structure of Double-Cation Perovskite Thin Films

2D/3D perovskite heterostructures have emerged as a promising material composition to reduce nonradiative recombination in perovskite-based LEDs and solar cells. Such heterostructures can be created by a surface treatment with large organic cations, for example, n-butylammonium bromide (BABr). To understand the impact of the BABr surface treatment on the double-cation (Cs 0.17 FA 0.83 Pb(I 0.6 Br 0.4 ) 3 ) (FA = formamidinium) perovskite thin film and further optimize the corresponding structures, an in-depth understanding of the chemical and electronic properties of the involved surfaces, interfaces, and bulk is required. We study the impact of the BABr treatment with a combination of surface-sensitive X-ray photoelectron spectroscopy and bulk-sensitive resonant inelastic soft X-ray scattering (RIXS). A quantitative analysis of the BABr-treated perovskite thin film shows a modified chemical perovskite surface environment of carbon, nitrogen, bromine, iodine, and lead, indicating that the treatment leads to a perovskite surface with a modified composition and bonding structure. With K-edge RIXS, the local environment at the nitrogen and carbon atoms is probed, allowing us to identify the presence of BABr in the perovskite bulk albeit with a modified bonding environment. This, in turn, identifies a "hidden parameter" for the optimization of the BABr treatment and overall performance of 2D/3D perovskite solar cell absorbers.

2D/3D perovskite heterostructure↗

Graph characterization of higher-order structure in atmospheric chemical reaction mechanisms

Atmospheric chemical reactions play an important role in air quality and climate change. While the structure and dynamics of individual chemical reactions are fairly well understood, the emergent properties of the entire atmospheric chemical system, which can involve many different species that participate in many different reactions, are not well described. In this work, we leverage graph-theoretic techniques to characterize patterns of interaction (“motifs”) in three different representations of gas-phase atmospheric chemistry, termed “chemical mechanisms.” These widely used mechanisms, the master chemical mechanism, the GEOS-Chem mechanism, and the Super-Fast mechanism, vary dramatically in scale and application, but they all generally aim to simulate the abundance and variability of chemical species in the atmosphere. This motif analysis quantifies the fundamental patterns of interaction within the mechanisms, which are directly related to their construction. For example, the gas-phase chemistry in the very small Super-Fast mechanism is entirely composed of bimolecular reactions, and its motif distribution matches that of an individual bimolecular reaction well. The larger and more complex mechanisms show emergent motif distributions that differ strongly from any specific reaction type, consistent with their complexity. The proposed motif analysis demonstrates that while these mechanisms all have a similar design goal, their higher-order structure of interactions differs strongly and thus provides a novel set of tools for exploring differences across chemical mechanisms.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Tuning the structural and antiferromagnetic phase transitions in UCr 2 Si 2 : Hydrostatic pressure and chemical substitution

Structural phase transitions in $\textit{f}$-electron materials have attracted sustained attention both for practical and basic science reasons, including the fact that they offer an environment to directly investigate relationships between structure and the $\textit{f}$-state. Here we present results for UCr 2 Si 2 , where structural (tetragonal → monoclinic) and antiferromagnetic phase transitions are seen at $T_S$ = 205 K and $T_N$ = 25 K, respectively. We also provide evidence for an additional second-order phase transition at $T_X$ = 280 K. We show that $T_X$, $T_S$, and $T_N$ respond in distinct ways to the application of hydrostatic pressure and Cr → Ru chemical substitution. In particular, hydrostatic compression increases the structural ordering temperature, eventually causes it to merge with $T_X$, and destroys the antiferromagnetism. In contrast, chemical substitution in the series UCr 2– x Ru x Si 2 suppresses both $T_S$ and $T_N$, causing them to approach zero temperature near $\textit{x}$ ≈ 0.16 and 0.08, respectively. The distinct $\textit{T–P}$ and ${T–x}$ phase diagrams are related to the evolution of the rigid Cr-Si and Si-Si substructures, where applied pressure semiuniformly compresses the unit cell, and Cr → Ru substitution results in uniaxial lattice compression along the tetragonal $\textit{c}$-axis and an expansion in the $\textit{ab}$-plane. These results in this work provide insights into an interesting class of strongly correlated quantum materials in which degrees of freedom associated with $\textit{f}$-electron magnetism, strong electronic correlations, and structural instabilities are readily controlled.

36 MATERIALS SCIENCE↗

Rational Selection of Transition-Metal Oxide Electrocatalysts from Structure Electronic Structure-Activity Relations: The Role of Defects, Strain, and Sub-Surface Layering

This BES research investigates the physicochemical properties of metal oxides and how they affect electrocatalytic functionalities. The goal is to develop a predictive framework for realizing top-performing electrocatalytic materials for energy-critical reactions. The hypothesis is that well-defined thin films allow detailed mapping of structural-activity relationships because flat surfaces are more straightforward to characterize. Furthermore, the well-defined nature of thin-film metal oxides allows precise tuning of structural and chemical variables for structure-activity-relationship mapping. The proposed research has two technical objectives. The first is to experimentally assess whether the binding energies of surface oxygen can serve as an activity descriptor for oxygen electrocatalysis on metal oxides and then how to control them by tuning the structure and chemical variables. The second is to find the rate-limiting process in oxygen electrocatalysis and other small-molecule reactions. Similar mechanistic insights have been developed on well-defined platinum surfaces but not yet on oxides. This research addresses this gap and uses electrochemistry and X-ray photoemission spectroscopy to study oxide surface chemistry. The obtained insights are collectively analyzed to reveal how the oxides’ structural and chemical variables affect kinetics and can be used to design more active electrocatalysts for energy-critical reactions.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

High pressure chemical reactivity and structural study of the Na–P and Li–P systems

In this work, the Na–P and Li–P chemical systems were studied under pressure using synchrotron X-ray diffraction in a diamond anvil cell up to 20 GPa, combined with the AIRSS ab initio random structure searching technique. The results reveal an enhanced reactivity of both alkali metals with phosphorous at slightly elevated pressures. This enables the synthesis of Li 3 P and Na 3 P at room temperature (RT) starting from element precursors, bypassing the established chemical synthesis methods. Both compounds undergo a pressure-induced phase transition from the hexagonal Na 3 As-type structure (stable at ambient conditions) towards a Fm m (FCC) structure that remains stable up to 20 GPa. Attempts to synthesize compounds with higher alkali metal content (such as Li 5 P) using high-temperature and -pressure conditions (up to 2000+ K and 30 GPa), inspired by recent theoretical predictions, were not successful.

25 ENERGY STORAGE↗

Synthesis, Structural Characterization and Chemical Bonding of Sr 7 Li 6 Sn 12 and its Quaternary Derivatives with Eu and Alkaline Earth Metal (Mg, Ca, Ba) Substitutions. A Tale of Seven Li‐Containing Stannides and Two Complex Crystal Structures

In this paper, we discuss the synthesis and the structural characterization of the new ternary compound Sr 7 Li 6 Sn 12 and its six quaternary derivatives, where alkaline earth metals (Ca, Mg, Ba) and the rare earth metal Eu are substituted, yielding crystalline phases of monoclinic or orthorhombic symmetry. The title compounds were synthesized via high‐temperature solid‐state reactions of the corresponding elements. The crystal structures were determined by single‐crystal X‐ray diffraction methods. The (Sr,Ca) 7 Li 6 Sn 12 and Eu 7 (Mg,Li) 6 Sn 12 phases represent a new structure type (space group P 2/ m , No. 10) while Sr 7 Li 6 Sn 12 and the rest of the title phases crystallize in the orthorhombic base‐centered space group Cmmm (No. 65) which is similar to the Eu 7 Li 8– x Sn 10+ x ( x ≈ 2.0) phase with the Ce 7 Li 8 Ge 10 structure type (Pearson code oC 50). Careful examination of the resulting structures shows intricate disordering between Li and Sn atoms, which is governed by the total number of valence electrons. The discussion of experimental results is also supported by DFT electronic structure calculations.

Osman, Hussien H.↗

Synoptic Mapping of Chemical Composition, Thermal Structure, and Air Motion from UARS Observations

An operational mapping algorithm was developed to process measurements of individual species observed by different satellite instruments on board UARS. Based on Fast Fourier Synoptic Mapping (FFSM), the algorithm accounts for the precessing orbit of UARS, the error of individual instruments, and gaps associated with instrument duty cycle and the satellite yaw maneuver. It provides synoptic structure and evolution on periods as short as 1 day, derived collectively from all observations of an individual species. The algorithm was applied to synoptically map temperature, thickness, and several chemical constituents observed by the instruments: MLS, CLAES, ISAMS, and HALOE. Each field variable observed by these instruments was mapped twice-daily in continuous global time series several months long. Mapped behavior produced via FFSM was compared against standard archived products generated via Kalman filtering. The standard map products reveal similar behavior, but are limited to features of larger scale. Tracer structure that develops through flow deformation and attending transport is therefore represented in those products more coarsely, eventually being sheared down to scales that are no longer represented properly. The synoptic time series also reveal a diurnal cycle for several of the constituents, one that emerges clearly in their space-time spectra. The zonal and meridional structure of diurnal variability was mapped by filtering the space-time spectrum, an intermediate product of FFSM, to those scales resolved by the UARS sampling. Geographical variations of the diurnal cycle have also been evaluated in its seasonal-mean structure by compositing distributions at individual local times. Both were compared to diurnal variations in chemical models and in dynamical models that account for transport by the diurnal tide. Diurnal variations were found to introduce spurious behavior into the archived products generated via Kalman filtering, behavior that is misrepresented in those synoptic time series. Aliasing by under-sampled diurnal variations introduces a bias into the time-mean structure of archived products. That systematic error is manifested as anomalous wave structure in the time-mean fields. By contrast, synoptic time series generated via FFSM faithfully represent such behavior as varying diurnally, so it does not corrupt time-mean structure. Tracer structure mapped via the above algorithm was being applied to determine the Brewer-Dobson circulation of the stratosphere through Lagrangian considerations. Preliminary results are encouraging: They reveal diabatic ascent in the tropics, balanced by diabatic descent over the winter hemisphere. This Lagrangian description of transport derived from UARS tracer measurements would be potentially valuable for diagnosing interannual changes of transport, specifically, in relation to interannual changes of total ozone. Regrettably, support was reduced to 50% of the approved funding level, leaving this component incomplete.

Salby, Murry L.↗