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At least 289 records · Page 16

Stratospheric Intrusion-Influenced Ozone Air Quality Exceedences Investigated in MERRA-2

Ozone near the surface is harmful to human health and is a result of the photochemical reaction with both man-made and natural precursor pollutant sources. Therefore, in order to reduce near surface ozone concentrations, communities must reduce anthropogenic pollution sources. However, the injection of stratospheric ozone into the troposphere, known as a stratospheric intrusion, can also lead to concentrations of ground-level ozone exceeding air quality standards. Stratospheric intrusions are dynamical atmospheric features, however, these intrusions have been misrepresented in models and reanalyses until recently, as the features of a stratospheric intrusion are best identified in horizontal resolutions of approximately 50 km or smaller. NASA's Modern-Era Retrospective Analysis for Research and Applications Version-2 (MERRA-2) reanalysis is a publicly-available high-resolution dataset (~50 km) with assimilated ozone that characterizes stratospheric ozone on the same spatiotemporal resolution as the meteorology. We show that stratospheric intrusions that impact surface air quality are well represented in the MERRA-2 reanalysis. This is demonstrated through a case study analysis of stratospheric intrusion events which were identified by the United States Environmental Protection Agency (EPA) to impact surface ozone air quality in spring 2012 in Colorado. The stratospheric intrusions are identified in MERRA-2 by the folding of the dynamical tropopause under the jet stream and subsequent isentropic descent of dry, O3-rich stratospheric air towards the surface where ozone air quality exceedences were observed. The MERRA-2 reanalysis can support air quality agencies for more rapid identification of the impact of stratospheric air on ground-level ozone.

Knowland, K. Emma↗

Isotopic Investigations of Nebular and Parent Body Processes with a High Sensitivity Ion Microprobe

NASA supported the development of the CAMECA ims 1270 ion microprobe at UCLA for applications in cosmochemistry. The primary investigations centered on measuring the microscopic distributions of key isotopic abundances in primitive meteoritic materials as a means of constraining the nature of important thermal and chemical processes in the solar nebula and the timescales associated with those processes. Our prior work on oxygen isotope anomalies in a wide variety of meteoritic materials had led us to a view of a spatially heterogeneous nebula, and in particular, a restricted region for CAI formation that is characterized by O-16-rich gas. Because of its production of CAIs in the energetic local environment near the protosun, the existence of a natural transport mechanism via bipolar outflows, and a general astrophysical plausibility, we were attracted to the fluctuating X-wind model which had been put forward by Frank Shu, Typhoon Lee, and colleagues. With our collaborators, we undertook a series of investigations to test the viability of this hypothesis; this work led directly to the discovery of live Be in CAIs and a clear demonstration of the existence of 160-rich condensates, which necessarily implies an O-16-rich gaseous reservoir in the nebula. Both of these observations fit well within the context of X-wind type models, i.e. formation of CAIs (or condensation of their precursors) in the reconnection ring sunward of the inner edge of the accretion disk, however much work remains to be done to test whether the physical parameters of the model can quantitatively predict not only the thermal histories of CAIs but also their radioactivity. The issue of spatial heterogeneity in the nebula, central to the X-wind model, is also at the heart of any chronology based on short-lived radioisotopes. In this work, we followed up on strong hints for presence of exireme:j: (53 day) short-lived Be-7, and have prepared a manuscript (in revision). We also measured A1-Mg systematics by a combined approach of high-precision multiple-collector SIMS analyses, traditional analyses on the UCLA ims 1270, and high-spatial resolution analyses using a NanoSIMS instrument. The data help to deconvolve effects due to partial resetting of the A1-Mg system by multiple thermal events. Finally, we initiated investigations related to nebular heterogeneity with a new initiative of in situ high-precision sulfur isotope analyses of sulfides from a wide variety of components of chondrites. The ultimate goal of all this work is to help develop a better understanding of the relationships between CAIs and chondrules, the astrophysical environments in which they formed, and the timescales of nebular processes. As detailed in Table 1, for the project period, 14 manuscripts were published and 17 abstracts were presented describing the work.

McKeegan, Kevin D.↗

Calculating the Height of Volcanic Cloud SO2 With a Lagrangian Trajectory Tool: Raikoke (2019) and Pinatubo (1991) Cases

We have developed a new data analysis tool to reconstruct the altitude of SO2 clouds ejected by avolcanic eruption. Starting with 2D fields of satellite observed SO2 column density, known volcanolocation, and reanalysis wind fields, the Goddard Lagrangian trajectory tool allows us to estimatethe altitude and local concentration of SO2 at the time of observation. We demonstrate this tool forthe June 21, 2019 Mt. Raikoke eruption (8h, 30h and 78 hours after eruption). We use SO2 data fromthe Ozone Mapping and Profiler Suite/Nadir Mapper (OMPS/NM) onboard the NASA-NOAASuomi National Polar Partnership satellite and the Tropospheric Monitoring Instrument(TROPOMI) onboard the European Copernicus Sentinel 5 precursor satellite and wind fields fromthe NASA Goddard Earth Observing System (GEOS) model. We obtained a wide distribution ofSO2 altitudes between 1 and 19 kilometers in different parts of the Raikoke SO2 clouds, with thehighest SO2 concentration between 11 and 16 km, in good agreement with data from independentSO2 layer height retrievals from TROPOMI and Infrared Atmospheric Sounding Interferometer(IASI). We then applied this method to the June 15, 1991 Mt. Pinatubo eruption using SO2 columnmeasurements from the NASA Total Ozone Mapping Spectrometer (TOMS) on June 16, 17, 18 andusing wind fields from the National Centers for Environmental Prediction Reanalysis version 2. Weobtained a wide distribution of SO2 heights from 6 km up to 30 km in the northern part of the cloud.We use our new trajectory tool to reconstruct volcanic SO2/aerosol emission sources as functions oftime and altitude, providing inputs to the GEOS model aerosol and chemistry schemes in order tosimulate the dispersion of volcanic SO2 and aerosol clouds from these events.

SO2↗

Photoenzymatic Csp 3 –Csp 3 bond formation via enzyme-templated radical–radical coupling

Cross-couplings are essential reactions in modern chemical synthesis, enabling the rapid construction of complex molecules from simple precursors. Transition metal catalysts are prized for these transformations because their reactivity and selectivity can be tuned via judicious selection of the metal and ligand. Although enzymes offer analogous opportunities for tuning via protein engineering, their application to cross-coupling remains limited, as nature relies on alternative paradigms for building molecular complexity. Here, we report the cross-coupling of alkyl halides and benzylic carboxylic acids using an engineered flavin-dependent lactate monooxygenase—a photoenzyme. The enzyme achieves this feat by exploiting the redox versatility of the flavin cofactor. Stoichiometric experiments, ultrafast spectroscopy, and computational studies support a mechanism in which photoexcited flavin quinone initiates the reaction via oxidative decarboxylation to generate a benzylic radical. The resulting flavin semiquinone can reduce the alkyl halide to form a second organic radical within the protein active site, which rapidly engages in C(sp 3 )–C(sp 3 ) bond formation. A variant was engineered to control the stereochemical outcome of this radical–radical coupling event, highlighting the ability of the protein to alter the energetic barrier for a mechanistic step that is traditionally understood to be near barrierless. This work demonstrates that the scope for nonnative reaction mechanisms in biocatalysis far exceeds previously established bounds and has potential to solve a variety of reactivity challenges in cross-coupling chemistry.

biocatalysis↗

Current Usage and Future Prospects of Multispectral (RGB) Satellite Imagery in Support of NWS Forecast Offices and National Centers

Current and future satellite sensors provide remotely sensed quantities from a variety of wavelengths ranging from the visible to the passive microwave, from both geostationary and low-Earth orbits. The NASA Short-term Prediction Research and Transition (SPoRT) Center has a long history of providing multispectral imagery from the Moderate Resolution Imaging Spectroradiometer (MODIS) aboard NASA s Terra and Aqua satellites in support of NWS forecast office activities. Products from MODIS have recently been extended to include a broader suite of multispectral imagery similar to those developed by EUMETSAT, based upon the spectral channel s available from the Spinning Enhanced Visible and InfraRed Imager (SEVIRI) aboard METEOSAT-9. This broader suite includes products that discriminate between air mass types associated with synoptic-scale features, assists in the identification of dust, and improves upon paired channel difference detection of fog and low cloud events. Similarly, researchers at NOAA/NESDIS and CIRA have developed air mass discrimination capabilities using channels available from the current GOES Sounders. Other applications of multispectral composites include combinations of high and low frequency, horizontal and vertically polarized passive microwave brightness temperatures to discriminate tropical cyclone structures and other synoptic-scale features. Many of these capabilities have been transitioned for evaluation and operational use at NWS Weather Forecast Offices and National Centers through collaborations with SPoRT and CIRA. Future instruments will continue the availability of these products and also expand upon current capabilities. The Advanced Baseline Imager (ABI) on GOES-R will improve the spectral, spatial, and temporal resolution of our current geostationary capabilities, and the recent launch of the Suomi National Polar-Orbiting Partnership (S-NPP) carries instruments such as the Visible Infrared Imager Radiometer Suite (VIIRS), the Cross-track Infrared Sounder (CrIS), and the Advanced Technology Microwave Sounder (ATMS), which have unrivaled spectral and spatial resolution, as precursors to the JPSS era (i.e., the next generation of polar orbiting satellites). At the same time, new image manipulation and display capabilities are available within AWIPS II, the next generation of the NWS forecaster decision support system. This presentation will present a review of SPoRT, CIRA, and NRL collaborations regarding multispectral satellite imagery and articulate an integrated and collaborative path forward with Raytheon AWIPS II development staff for integrating current and future capabilities that support new satellite instrumentation and the AWIPS II decision support system.

Molthan, Andrew L.↗

Influence of Thermal Treatment on Preceramic Polymer Grafted Nanoparticle Network Formation: Implications for Thermal Protection Systems and Aerospace Propulsion Components

Preceramic polymer grafted nanoparticles (PCP GNPs) offer potential advantages in the production of polymer-derived ceramic composites compared to neat preceramic polymers (PCPs), such as reduced thermal shrinkage and increased char yield. In comparison to traditional composites (particles + free polymer), PCPs avoid issues of compatibility, agglomeration, and phase separation during processing and provide routes to control nanoparticle arrangement. Prior literature has established that the conversion efficiency of PCPs and PCP GNPs to ceramics and ceramic composites is linked to the thermal pretreatment of these precursor polymers (e.g., curing). In this paper, we investigate the material transformations that occur when exposing PCP GNPs to a low-temperature thermal treatment (≤250 °C) prior to pyrolysis. The PCP GNPs explored in this study possessed silica nanoparticle cores but were distinct in their PCP coronas, having poly(1,1-dimethylpropylsilane) (allyl-GNP)- or poly(1,1-dimethylbenzylethylsilane) (styryl-GNP)-grafted polymers. After undergoing low-temperature thermal treatment, these PCP GNPs exhibited increased char yield at 800 °C; however, unlike commercial PCPs (e.g., allylhydridopolycarbosilane (SMP-10)), obvious cross-linkable sites are not present in the PCP corona structure. Differential scanning calorimetry, oscillatory rheology, and X-ray photon correlation spectroscopy were utilized to elucidate the thermally induced material changes in the allyl- and styryl-GNPs. Thermally induced changes to the structure and behavior of the PCP GNPs were determined to be linked to the chemical structure of the grafted polycarbosilane chains. Styryl-GNPs experienced a curing event between 180 and 250 °C, effecting the formation of a network, which contributed to char yield improvement (at 800 °C). The nanoscale dynamics of this material also shows a transition from diffuse behavior to ballistic behavior because of the cross-linking event. Conversely, the allyl-GNPs did not exhibit a curing event under heat treatment but did show an increase in thermally induced physical cross-linking. The allyl-GNP physical network is stronger after the first cycle of thermal treatment, and it is considered that this contributed to the improvement in char yield post thermal treatment. The advancements in the understanding of the cross-linking behavior of these hybrid materials are expected to advance the application of these materials to turbine engine, advanced friction, and heat-shielding components.

36 MATERIALS SCIENCE↗

Experimental Studies on the Effect of Impact Processes on the Formation and Evolution of Amino Acids

Introduction: A critical step in the emergence of life on Earth was the synthesis of larger organic molecules from simple building blocks such as NH3, CO2, H2O, and CH3OH. The presence of amino acids and other complex organics in comets and meteorites demonstrates that widespread organic synthesis likely occurred across the early solar system. Building on previous work [e.g., 1-3], we systematically explore impact-driven chemical evolution of exogenous organics and their precursors. Collisional processes may also have provided a source of energy for the formation of more complex organics from endogenous building blocks. The high flux of impactors to Earth immediately prior to and during the origins of life suggests that impacts could have played a critical role. Key Questions: 1. How are the formation and evolution of amino acids affected by the presence of a mineral matrix during cometary and asteroidal impacts onto the early Earth? 2. Do some minerals (e.g., phyllosilicates) provide a more robust protective framework or reactive surface site for amino-acid formation and/or polymerization? 3. Does the abundance of ices and/or amino acids relative to that of the mineral matrix affect the formation and evolution of amino acids? 4. Are there impact velocities/shock pressures at which formation or polymerization of amino acids is favored or precluded? Experimental Approach: This study systematically examines the conditions under which amino acids and other organic molecules can form, be polymerized, and/or be destroyed during impact events into particulate regolith simulants. Variable parameters include the modal composition of this regolith (silicate matrices, ratios of ices, silicates, and amino acids) and impact velocities/shock pressures. Impacts experiments were performed using the two-stage light-gas gun (LGG), vertical gun (VG), and flat-plate accelerator (FPA) in the Experimental Impact Lab at JSC. FPA experiments were performed over a range of shock pressures (11.3-31.5 GPa) using CM chondrite simulant mixed with amino acids at ratios of 0:10, 1:10, 1:103, and 1:106 (amino acid:host). Techniques for mixing cometary ices have been optimized and test runs have been performed using the LGG (see figure below). Analysis: Post-impact, samples are heated in water to extract amino acids and peptides. Extracts are characterized via liquid chromatography-mass spectrometry (LC-MS) and the mineralogies of solid residues are characterized using X-ray diffraction, scanning electron microscopy and transmission electron microscopy. Additional LC-MS and mineralogical analyses are underway.

Eve L Berger↗

Revolutionary Concepts for Human Outer Planet Exploration (HOPE)

This paper summarizes the content of a NASA-led study performed to identify revolutionary concepts and supporting technologies for Human Outer Planet Exploration (HOPE). Callisto, the fourth of Jupiter's Galilean moons, was chosen as the destination for the HOPE study. Assumptions for the Callisto mission include a launch year of 2045 or later, a spacecraft capable of transporting humans to and from Callisto in less than five years, and a requirement to support three humans on the surface for a minimum of 30 days. Analyses performed in support of HOPE include identification of precursor science and technology demonstration missions and development of vehicle concepts for transporting crew and supplies. A complete surface architecture was developed to provide the human crew with a power system, a propellant production plant, a surface habitat, and supporting robotic systems. An operational concept was defined that provides a surface layout for these architecture components, a list of surface tasks, a 30-day timeline, a daily schedule, and a plan for communication from the surface.

Power electronics↗

Sulfuric Acid New Particle Formation Field Campaign Report

This campaign aimed to measure gaseous sulfuric acid concentrations at the surface level using a newly developed sulfuric acid dimethylamine-reactive condensation particle counter (SAD-RCPC). Sulfuric acid is a key nucleation precursor and is the likely driving compound for new particle formation at the Atmospheric Radiation Measurement (ARM) user facility’s Southern Great Plains (SGP) observatory. The SAD-RCPC will be deployed in the future at ARM SGP (AFC010010: "Vertically Resolved Nucleation Precursors at SGP") scheduled for 2024. The campaign was in conjunction with Eleanor Browne's campaign (AFC010075: Boundary-layer gradients in new particle formation) and took place from 05/7/23 to 5/21/23. The measured sulfuric acid concentrations by the SAD-RCPC will be compared to concentrations measured by Browne's chemical ionization mass spectrometer (CIMS). The SAD-RCPC consisted of a glass flow reactor coupled to a 1-nm diethylene glycol condensation particle counter (DEG CPC). Sampled air was mixed with a high concentration of dimethylamine vapor (~1 ppbv). Sulfuric acid within the sampled gas nucleated with dimethylamine to form detectable 1-nm particles. The measured particle concentration was converted to sulfuric acid concentration using nucleation reaction kinetics. The pulse height distribution of particles detected by the DEG CPC was observed using a multi-channel analyzer. Large pre-existing particles were separated from the freshly formed particles in the SAD-RCPC from the pulse height distribution (PHD). During the short campaign, seven new particle formation events were observed. The SAD-RCPC detected an increase in sulfuric acid concentration, but this also coincided with an increase in pre-existing <3 nm particle concentrations. In addition, Browne's CIMS detect sulfuric acid concentrations in the range of 10 5 -10 6 cm -3 .

54 ENVIRONMENTAL SCIENCES↗

Design, Manufacture and Test of Cryotank Components

On the composite cryotank technology development (CCTD) project, the Boeing Company built two cryotanks as a means of advancing technology and manufacturing readiness levels (TRL and MRL) and lowering the risk of fabricating full-scale fuel containment vessels.1 CCTD focused on upper stage extended duration applications where long term storage of propellants is required. The project involved the design, analysis, fabrication, and test of manufacturing demonstration units (MDU), a 2.4 m (precursor) and a 5.5 m composite cryotank. Key design features included one-piece wall construction to minimize overall weight (eliminating the need for a bellyband joint), 3-dimensionally (3D) reinforced y-joint material to alleviate stress concentrations at the tank to skirt interface and a purge-able fluted core skirt to carry high axial launch loads. The tanks were made with OoA curing pre-impregnated (prepreg) carbon/epoxy (C/E) slit-tape tow (STT) that contained thin micro-crack resistant plies in the tank wall center to impede permeation. The tanks were fabricated at Boeing's Seattle-based Advanced Development Center (ADC) using RAFP and multipiece break-down tooling. The tooling was designed and built by Janicki Industries (JI) at Sedro Woolley, Washington. Tank assemblage consisted of co-bonded dome covers, one-piece fluted core skirts and mechanical fastened cover/sump. Ultrasonic inspection was performed after every cure or bond and a structural health monitoring system (SHMS) was installed to identify potential impact damage events (in-process and/or during transportation). The tanks were low temperature tested at NASA's George C. Marshall Space Flight Center (MSFC) in Huntsville, Alabama. The testing, which consisted of a sequence of fill/drain pressure and thermal cycles using LH2, was successfully concluded in 2012 on the 2.4 m tank and in 2014 on the 5.5 m tank. Structural, thermal, and permeation performance data was obtained. 2 Critical design features and manufacturing advancements, which helped to validate 25% weight and 30% cost reduction projections, were matured. These advancements will help to guide future composite tank integration activities on next generation long duration aircraft and space launch vehicles. Because CCTD addressed innovative design features, heavy lift size scale-up, multipiece captured tooling, new generation automated material placement (AMP) equipment and OoA materials, this chapter should be of interest to educators, students and manufacturers of composite hardware and flight vehicles.

McCarville, Douglas A.↗

The Relative Reactivity of Deoxyribose and Ribose: Did DNA Come Before RNA?

If it is assumed that there was a precursor to the ribose-phosphate backbone of RNA in the preRNA world (such as peptide nucleic acid), then the entry of various sugars into the genetic material may be related to the stability and non-enzymatic reactivity of the aldose. The rate of decomposition of 2-deoxyribose has been determined to be 1/3 that of ribose. In addition we have measured the amount of free aldehyde by H-1 and C-13 NMR and find that it has approximately 0.15% free aldehyde compared to 0.05% for ribose at 25 C. This suggests that deoxyribose would be significantly more reactive with early bases in the absence of enzymes. This is confirmed by urazole and deoxyribose reacting to form the deoxynucleoside 45 times faster as 25 C than urazole reacts with ribose to form the Ribonucleoside. Urazole is a potential precursor of uracil and is a plausible prebiotic compound which reacts with aldoses to form nucleosides. Thus the non-enzymatic reactivity of deoxyribose would favor its early use over ribose until enzymes could change the relative reactivities. Most of the reasons that RNA is presumed to have come before DNA are extrapolations back from contemporary metabolism (e.g. the abundance of ribose based coenzymes, the biosynthesis of histidine, deoxyribonucleotides are synthesized from ribonucleotides, etc.). It is very difficult to reconstruct biochemical pathways much before the last common ancestor, and it is even more difficult to do more than guess at the biochemistry of very early self-replicating systems. Thus we believe that these reasons are not compelling and that the non-enzymatic chemistry may be more important than enzymatic pathways for constructing the earliest of biochemical pathways. While the RNA world has been discussed at great length, there has not been an exploration of the transition out of the RNA world. We have constructed many possible schemes of genetic takeover events from preRNA to modern DNA, RNA, protein system which could generate the RNA metabolic fossils we see today.

Dworkin, Jason P.↗

Catalytic Upgrading of Renewable Feedstock (Final Technical Report)

The goal of this DOE-funded project was to investigate the fundamental science related to the development of homogeneous (de)hydrogenation catalysts in order to enable energy-relevant transformations of bio-relevant chemical feedstocks including ethanol. The primary focus was to improve the activity of ethanol upgrading catalysts, specifically informed through mechanistic studies, in order to enable rational design optimization strategies. Following in depth mechanistic studies, targeted reaction optimization approaches included ligand redesign to improve catalyst stability, developing new carbon-carbon bond forming reactions using ethanol as a precursor, and examining photochemically-mediated reactions, ultimately to integrate within other reactor designs such as continuous flow reactors. The high modularity of the catalyst components (ligands) has enabled the preparation and analyses of multiple catalyst precursors. These studies uncovered an unexpectedly beneficial substitution pattern of the ligand structure that led to the development of new catalysts that are the best in class for upgrading ethanol to butanol with a turnover number of 155,890 and a turnover frequency of 12,690 h –1 . In addition to upgrading ethanol to butanol, cascade reaction sequences were developed to form new C-C bonds using ethanol as a bio-relevant feedstock, providing access to platform chemicals from renewable sources. As part of the reaction discovery process, new mechanistic details were uncovered that provided insights into: a) catalyst speciation, b) decomposition pathways, c) carbon monoxide releasing pathways, and d) carbon-carbon and carbon hydrogen bond breaking pathways. Most of these outcomes were previously not known; however, they provide important directions for new catalyst design strategies. Finally, use of high throughput and in situ photochemical reaction analyses enabled detailed studies into changes to the catalyst structure upon irradiation. Irradiation was found to improve hydrogen transfer catalysis, by promoting a ligand dissociation event.

09 BIOMASS FUELS↗

Illustrating the Spatiotemporal Complexity of No2 Columns Using A Multi-Perspective Observing System: Moving Toward Geostationary Product Validation and Applications

As a precursor to secondary pollutants like ozone and PM2.5, nitrogen dioxide (NO2) is crucial to understand when addressing air quality issues. However, due to NO2’s short lifetime during the daytime and complexity of emission sources in urbanized regions, interpreting datasets from ground or satellite perspectives alone are challenged by variance in spatial and temporal resolutions. High resolution airborne mapping (< 1 km) of NO2 column densities across morning, midday, and afternoon add a unique perspective toward interpreting satellite data with respect to ground-measurements. This presentation focuses on the interpretation of spatiotemporal complexity of NO2 columns from the Synergistic TEMPO Air Quality Science Study (STAQS). The mission’s goal is to integrate geostationary observations from Tropospheric Emissions: Monitoring of Pollution (TEMPO) with traditional and enhanced air quality monitoring to improve the understanding of air quality science for increased societal benefit. We will demonstrate the interweaved perspective of NO2 columns from ground-based Pandora spectrometers and satellite-based observations (e.g., TROPOMI) as compared to high spatial resolution airborne observations from the GEOstationary Coastal and Air Pollution Events (GEO-CAPE) Airborne Simulator (GCAS). This includes the evaluation of each dataset through comparison to each other to identify potential biases in data products and the impact of heterogeneity on these comparisons. Airborne data will also be used as a proxy for geostationary observations with morning, midday, and afternoon raster maps collected over four cities (Los Angeles, Chicago, Toronto, and New York City). Finally, recent research outcomes will be presented to demonstrate how airborne and geostationary observations can be used to evaluate emission inventories and air quality models.

Laura Judd↗

The Ozone Water-Land Environmental Transition Study: An Innovative Strategy for Understanding Chesapeake Bay Pollution Events

Coastal regions have historically represented a significant challenge for air quality investigations because of water-land boundary transition characteristics and a paucity of measurements available over water. Prior studies have identified the formation of high levels of ozone over water bodies, such as the Chesapeake Bay, that can potentially recirculate back over land to significantly impact populated areas. Earth-observing satellites and forecast models face challenges in capturing the coastal transition zone where small-scale meteorological dynamics are complex and large changes in pollutants can occur on very short spatial and temporal scales. An observation strategy is presented to synchronously measure pollutants “over land” and “over water” to provide a more complete picture of chemical gradients across coastal boundaries for both the needs of state and local environmental management and new remote sensing platforms. Intensive vertical profile information from ozone lidar systems and ozonesondes, obtained at two main sites, one over land and the other over water, are complemented by remote sensing and in situ observations of air quality from ground-based, airborne (both personned and unpersonned), and shipborne platforms. These observations, coupled with reliable chemical transport simulations, such as the National Oceanic and Atmospheric Administration (NOAA) National Air Quality Forecast Capability (NAQFC), are expected to lead to a more fully characterized and complete land–water interaction observing system that can be used to assess future geostationary air quality instruments, such as the National Aeronautics and Space Administration (NASA) Tropospheric Emissions: Monitoring of Pollution (TEMPO), and current low-Earth-orbiting satellites, such as the European Space Agency’s Sentinel-5 Precursor (S5-P) with its Tropospheric Monitoring Instrument (TROPOMI).

Forecast Models↗

Sudbury project (University of Muenster-Ontario Geological Survey): Sr-Nd in heterolithic breccias and gabbroic dikes

One major objective of our Sudbury project was to define origin and age of the huge breccia units below and above the Sudbury Igneous Complex (SIC). The heterolithic Footwall Breccia (FB) represents a part of the uplifted crater floor. It contains subrounded fragments up to several meters in size and lithic fragments with shock features (greater than 10 GPa) embedded into a fine- to medium-grained matrix. Epsilon(sub Nd)-epsilon(sub Sr) relationships point to almost exclusively parautochthonous precursor lithologies. The different textures of the matrix reflect the metamorphic history of the breccia layer; thermal annealing by the overlying hot impact melt sheet (SIC) at temperatures greater than 1000 C resulted in melting of the fine crushed material, followed by an episode of metasomatic K-feldspar growth and, finally, formation of low-grade minerals such as actinolite and chlorite. Isotope relationships in the Onaping breccias (Gray and Green Member) are much more complex. All attempts to date the breccia formation failed: Zircons are entirely derived from country rocks and lack the pronounced Pb loss caused by the heat of the slowly cooling impact melt sheet (SIC). Rb-Sr techniques using either lithic fragments of different shock stages or the thin slab method, set time limits for the apparently pervasive alkali mobility in these suevitic breccias. The data array and the intercept in the plots point to a major Rb-Sr fractionation around 1.54 Ga ago. This model age is in the same range as the age obtained for the metasomatic matrix of the FB. Rb-Sr dating of a shock event in impact-related breccias seems to be possible only if their matrix had suffered total melting by the hot melt sheet (FB) or if they contain a high fraction of impact melt (suevitic Onaping breccias), whereas the degree of shock metamorphism in rock or lithic fragments plays a minor role. In the Sudbury case, however, the impact melt in the seuvitic breccias is devitrified and recrystallized, which changed Rb/Sr ratios quite drastically. Therefore, the Onaping breccias give only age limits for alteration and low-grade metamorphism. The Sm-Nd system was not reset during the Sudbury event; clasts as well as the matrix in the FB and in the Onaping breccias show preimpact 'Archean' Nd isotope signatures.

Buhl, D.↗

Timing of Formation of a Wassonite-bearing Chondrule

Wassonite, ideally stoichiometric TiS, is a titanium monosulfide recently discovered in the Yamato 691 EH3 enstatite chondrite. Wassonite grains were located within the mesostasis of a single barred olivine chondrule. Such chondrules likely formed in the solar nebula by melting of fine grained precursor dust. The reduced nature of enstatite chondrites, and the wassonite-bearing chondrule in particular, may suggest precursor materials included Ti-bearing troilite, metallic Fe-Ni, and possibly graphite. Under the reducing conditions present in enstatite chondrites S can partition more readily into silicate melt, leading to raised Ti content of the residual Fe-FeS melt. By the time sulfide crystallized from the melt, the Ti concentration was high enough to form small grains of pure TiS - wassonite. As a mineral not previously observed in nature wassonite and its host chondrule may provide additional constraints on physical and chemical conditions in the solar nebula at a specific time and location relevant to planetary formation. Enstatite chondrites and Earth share similar isotopic compositions of Cr, Ni, Ti, O and N. Understanding the formation conditions of enstatite chondrite chondrules may therefore have wider relevance for terrestrial planet accretion and other early inner solar system processes. Here we present preliminary results of an investigation of the Al-Mg systematics of the only known wassonite-bearing chondrule. The goal of this study is to determine whether this chondrule's formation was contemporaneous with other enstatite chondrite chondrules and to establish its place in the broader timeline of solar system events.

Needham, A. W.↗

Automated Discovery of Flight Track Anomalies

As new technologies are developed to handle the complexities of the Next Generation Air Transportation System (NextGen), it is increasingly important to address both current and future safety concerns along with the operational, environmental, and efficiency issues within the National Airspace System (NAS). In recent years, the Federal Aviation Administration’s (FAA) safety offices have been researching ways to utilize the many safety databases maintained by the FAA, such as those involving flight recorders, radar tracks, weather, and many other high- volume sensors, in order to monitor this unique and complex system. Although a number of current technologies do monitor the frequency of known safety risks in the NAS, very few methods currently exist that are capable of analyzing large data repositories with the purpose of discovering new and previously unmonitored safety risks. While monitoring the frequency of known events in the NAS enables mitigation of already identified problems, a more proactive approach of finding unidentified issues still needs to be addressed. This is especially important in the proactive identification of new, emergent safety issues that may result from the planned introduction of advanced NextGen air traffic management technologies and procedures. Development of an automated tool that continuously evaluates the NAS to discover both events exhibiting flight characteristics indicative of safety-related concerns as well as operational anomalies will heighten the awareness of such situations in the aviation community and serve to increase the overall safety of the NAS. This paper discusses the extension of previous anomaly detection work to identify operationally significant flights within the highly complex airspace encompassing the New York area of operations, focusing on the major airports of Newark International (EWR), LaGuardia International (LGA), and John F. Kennedy International (JFK). In addition, flight traffic in the vicinity of Denver International (DEN) airport/airspace is also investigated to evaluate the impact on operations due to variances in seasonal weather and airport elevation. From our previous research, subject matter experts determined that some of the identified anomalies were significant, but could not reach conclusive findings without additional supportive data. To advance this research further, causal examination using domain experts is continued along with the integration of air traffic control (ATC) voice data to shed much needed insight into resolving which flight characteristic(s) may be impacting an aircraft's unusual profile. Once a flight characteristic is identified, it could be included in a list of potential safety precursors. This paper also describes a process that has been developed and implemented to automatically identify and produce daily reports on flights of interest from the previous day.

Matthews, Bryan↗

Tropical Tropospheric Ozone Trends (1990 to 2022): A Re-evaluation Based on SHADOZ and IAGOS Profiles and TOMS/OMI Columns

Changes in tropical tropospheric ozone (TTO) are of importance because this region spans roughly a third of the Earth and portions of it are experiencing variability in trends of ozone precursors (CO, NO x , CH 4 and nonmethane hydrocarbons) associated with economic growth and fires. In addition to ozone changes affecting radiative forcing, tropical ozone is an important source of the OH radical and thus, the oxidizing capacity of the planet (Thompson, 1992). Recent studies examining TTO trends satellite and in-situ observations over the past ~25 years include: Thompson et al., JGR, 2021; Gaudel et al., ACP, 2023; Stauffer et al., ACP, 2023. The results show considerable regional and seasonal variability in TTO trends and sensitivity to data selection, frequency, and statistical method used. The satellite data vary most widely in method, time period and reliability. Here we revisit trends for the 1990-2022 period with the best-characterized buv-based satellite products that span that period (derived from TOMS and OMI, Ziemke et al., 2019). The satellite-based trends are compared to trends based on in-situ data from the Southern Hemisphere Additional Ozonesondes (SHADOZ) network (1998-2022), measurements from selected pre-SHADOZ and IAGOS commercial aircraft data (Gaudel et al., 2023). Among sensitivities examined are the dependence of ozone trends on start and end years, impacts of ENSO events and the COVID-19 perturbation to emissions. Two statistical methods are used, quantile regression (QR) and multiple linear regression (MLR). Trends of total TTO, ozone segments in the boundary layer (to ~700 hPa), and free troposphere (700-300 hPa) are compared.

ozone, OMI, tropospheric ozone, SHADOZ↗