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Anomalous DOC Signatures Reveal Iron Control on Export Dynamics in the Pacific Southern Ocean

Here we shed light on two mechanisms that stimulate deep particle export via upper-ocean iron fertilization in the Southern Ocean: deep frontal mixing and melting of sea ice. We present data collected a decade apart in the Pacific sector of the Southern Ocean when, serendipitously, seasonal Antarctic ice melt was anomalously low (2008) and anomalously high (2017). In 2008, the low ice melt year, we concluded that vertical mixing of iron into the euphotic zone via deep-mixing fronts was the primary stimulant of export that reached depths of ~1500 meters. This process was evidenced by localized enhancements of dissolved organic carbon (DOC) concentrations up to 4 μmol C kg-1 beneath seven branches of fronts embedded within the Antarctic Circumpolar Current (ACC). We used these enhanced DOC concentrations in the bathypelagic as primary indications of the depths and locations of recent export, as it is a logical residue of such. In 2017, the year in which sea ice melt was anomalously high, we concluded that the main driver of a widespread export event to the seafloor was the lateral influx of iron within the melt. Indications of this event included substantial enhancements of DOC concentrations (2 - 31 6 μmol C kg-1), elevated beam attenuation, and enhanced surface iron concentrations associated with a layer of low salinity water at a nearby station. Further, significant deficits of upper ocean silicic acid during the 2017 occupation indicated that deep export was likely stimulated by an iron-fueled diatom bloom. This analysis highlights the impact of iron supplied from frontal vertical mixing and sea ice melt on export and ultimately for long-term carbon sequestration in the Southern Ocean, as well as the utility of deep DOC enrichments as signatures of particle export. Understanding the impact that ice melt events have on carbon export is crucial given that anomalous events are occurring more often as our climate changes.

Dissolved Organic Carbon↗

Geomorphic processes active in the Southwestern Louisiana Canal, Lafourche Parish, Louisiana

The geomorphological changes causing the destruction of the banks of the Southwestern Louisiana Canal are studied by means of field work, laboratory analyses, and infrared color imagery interpretation. Turbulence and flow patterns are mapped, and related to erosion and sediment deposition processes. The accelerated erosion rate of the last decade is discussed, with two causative factors cited: (1) development of faster boats, increasing bank and bottom erosion, and (2) a subsequently larger tidal influx, with greater erosive ability. The physical properties of the canal bank materials are also analyzed. It is concluded that channel erosion progressively increases, with no indications of stabilization, until they merge with other waterways and become indistinguishable from natural water bodies.

Doiron, L. N.↗

Limits to Cloud Susceptibility

1-kilometer AVHRR observations of ship tracks in low-level clouds off the west coast of the U S. were used to determine limits for the degree to which clouds might be altered by increases in anthropogenic aerosols. Hundreds of tracks were analyzed to determine whether the changes in droplet radii, visible optical depths, and cloud top altitudes that result from the influx of particles from underlying ships were consistent with expectations based on simple models for the indirect effect of aerosols. The models predict substantial increases in sunlight reflected by polluted clouds due to the increases in droplet numbers and cloud liquid water that result from the elevated particle concentrations. Contrary to the model predictions, the analysis of ship tracks revealed a 15-20% reduction in liquid water for the polluted clouds. Studies performed with a large-eddy cloud simulation model suggested that the shortfall in cloud liquid water found in the satellite observations might be attributed to the restriction that the 1-kilometer pixels be completely covered by either polluted or unpolluted cloud. The simulation model revealed that a substantial fraction of the indirect effect is caused by a horizontal redistribution of cloud water in the polluted clouds. Cloud-free gaps in polluted clouds fill in with cloud water while the cloud-free gaps in the surrounding unpolluted clouds remain cloud-free. By limiting the analysis to only overcast pixels, the current study failed to account for the gap-filling predicted by the simulation model. This finding and an analysis of the spatial variability of marine stratus suggest new ways to analyze ship tracks to determine the limit to which particle pollution will alter the amount of sunlight reflected by clouds.

Coakley, James A., Jr.↗

Organic geochemistry of sediments from the continental margin off southern New England, U.S.A.--Part II. Lipids

Organic geochemical measurements of the lipid fraction, comparing saturated and aromatic hydrocarbons, fatty acids, alcohols and sterols, have been carried out on six sediments cores collected from the Atlantic shelf, slope and the rise areas to evaluate the cross-shelf transport of the organic carbon. The concentration of most of the organic compound classes studied is correlated with the total organic carbon, which decreases from the shelf through slope to the rise. Terrigenous carbon is recognizable even in the slope and rise sediments, but terrestrial influx decreases relative to marine generated lipids in the slope and rise organic matter. We estimate that approximately 50% of the shelf organic matter is exported to the slope. Data of sediment trap material collected at 1200 m from 1250 m water depth are discussed and compared with that of surface sediment from 1280 m water depth (slope). Fluxes for specific organic compound classes have been computed. The fluxes are of the same magnitude as for equatorial North Atlantic trap particulates at comparable water depth, studied by other investigations.

NASA Discipline Exobiology↗

Kabbaldurga-type charnockitization: A local phenomenon in the granulite to amphibolite grade transition zone

In the deeply eroded Precambrian crust of South India and Sri Lanka, a series of spectacular exposures shows progressive development of coarse-grained charnockite through dehydration of amphibolite grade gneisses in different arrested stages. At Kabbaldurga, charnockitization of Archaean grey biotite-hornblende gneisses occurred about 2.5 Ga ago and evidently was induced by the influx of external carbonic fluids along a system of ductile shears and the foliation planes. The results of oxygen isotope thermometry and of geothermobarometry in adjacent areas indicate a P-T regime of 700 to 750 C and 5 to 7 kb. The decrease of water activity in the fluid infiltrated zones caused an almost complete breakdown of hornblende and biotite and the new growth of hypersthene. Detailed petrographic and geochemical studies revealed marked changes in mineralogy and chemistry from granodioritic to granitic which document the metasomatic nature of the process.

Raith, M.↗

Assessing Carbon Properties in Coastal Waters with a New Observing System Testbed

Large rainfall events over land can lead to a substantial flux of carbon and nutrients to estuaries and the coastal ocean. In the mid-Atlantic on the east coast of North America (35° - 42° N), these events often happen due to tropical storm activity as well as less predictable anomalously large midlatitude storms or abrupt spring snow melt runoff. Storms can directly impact the coastal carbon cycle via export of carbon from land to sea, while also stimulating phytoplankton production due to the influx of nutrients to the coastal ocean. To assess the impact of high precipitation and river flow events on the coastal carbon cycle, we have integrated multiple observing platforms in an analytical framework to dynamically observe carbon-related properties. The new observing system testbed (NOS-T) allows for an estimate of phytoplankton and organic carbon stocks in the surface ocean, with a goal of providing near real time analytical capability. A case study of high river discharge in the mid-Atlantic in the summer and fall of 2018 and 2021 were used to examine how riverine carbon manifests along the land-estuary-ocean continuum particularly in Chesapeake Bay. Chesapeake Bay was chosen as the study site because of long term monitoring by the Chesapeake Bay Program and a robust and well-developed regional biogeochemical modeling system, the Chesapeake Bay Environmental Forecast System (CBEFS), that is publicly available. There is also new capability in Chesapeake Bay to combine hyperspectral radiometric data from the Aerosol Robotic Network site that is online in 2022 with in-water observations of optical properties. Precipitation data from the Global Precipitation Measurement IMERG data set was used to establish triggering criteria for storm carbon flux observation. USGS and in-water carbon data were used to establish statistical models to estimate the mass flux of organic carbon into Chesapeake Bay using measured river discharge. The year 2018 was examined as there was record rainfall and near record river flow in the late summer. The CBEFS modeling was compared with in-water estimates of dissolved organic carbon (DOC) to assess the model’s ability to capture storm fluxes of carbon to the ecosystem. Multiple satellite platforms were also used to assess how remote sensing using passive Earth orbiting sensors can be used to observe carbon in this complex coastal region. A set of recommendations have been established to improve sensing capability to measure aquatic carbon during storm events. A unique challenge in these dynamic inland waters is how rapidly carbon fluxes can evolve in space and time, with many sources contributing to the water leaving reflectance that satellites can observe. To improve our ability to quantify carbon stocks and fluxes in near real time, a suite of satellite sensors and high-resolution modeling capability is needed, all supplemented by in situ monitoring. Future inclusion of in-water observations that would be deployed when the system reaches triggering criteria, as well as taskable orbital instruments, will improve estimates of ocean carbon properties and provide the ability to calculate major carbon stocks and fluxes in near real time following episodic storm events.

land-ocean continuum↗

Uptake and speciation of trace metal inputs to Wetland Soils from Illinois and South Carolina and Stream Sediments from Tennessee

Metals occur in all ecosystems, although their concentrations vary depending on their natural geologic conditions and surrounding human activities. In addition to metals intrinsically present from the geology of a particular system, metals can enter environmental systems from a wide variety of natural and anthropogenic sources, such as sediment re-suspension, mining operations, industrial processes, agricultural activities, and atmospheric deposition. While metals can be toxic at high concentrations, some metals serve as essential micronutrients for biogeochemical processes. Metal transport and availability in engineered and natural water systems depend on processes of adsorption/desorption, oxidation/reduction, dissolution/precipitation, and ligand complexation. Insights into the speciation of metals and their bioavailability will also help advance understanding of the roles of metals in the biogeochemical cycling of nutrients. We conducted batch experiments under anoxic conditions on soils and sediments collected from three different natural aquatic systems to understand their response to influxes of dissolved Cu, Ni and Zn. While soils and sediments from all sites could strongly bind added trace metals, there were substantial differences in trace metal uptake trends between different sites, especially for Cu. There was no distinct correlation between trace metal uptake and the total organic matter, iron, and sulfur content present in the samples. X-ray absorption spectroscopy indicated that the speciation of the freshly added metals taken up by the solids differs substantially from the speciation of the metals originally present in unamended samples. Cu sulfides dominated speciation at low loadings (1 µmol/g), whereas complexation to thiol groups and formation of metallic Cu governed speciation at high loadings (10 µmol/g). For Ni and Zn, adsorption to mineral surfaces and organic matter governed their speciation in materials from most sites. This study suggests that the background speciation of metals in natural aquatic systems is a poor predictor of the speciation and lability of metals introduced to terrestrial aquatic systems from anthropogenic or natural processes. Our findings imply that geochemical processes controlling trace metal speciation may vary considerably with metal loading in different natural systems. Data are provided for marsh wetland soils at Argonne National Laboratory (Marsh 1 and Marsh 2), riparian wetland soils (Riparian 1 and Riparian 2) in the Tims Branch watershed at Savannah River National Laboratory, and stream bed sediments (Stream 1 and Stream 2) from East Fork Poplar Creek near Oak Ridge National Laboratory. Data package includes the results of trace metal uptake experiments conducted on the selected sites for determining their capacity to immobilize metals under different loadings. XANES spectra for Cu, Ni, ad Zn at different loadings are included in the package. The abundance of different trace metal species obtained using linear combination fitting in ATHENA are also included in the data.

54 ENVIRONMENTAL SCIENCES↗

Erosion of Volatiles by Micro-Meteoroid Bombardment on Ceres, and Comparison to the Moon and Mercury

Ceres, the largest reservoir of water in the main-belt, was recently visited by the Dawn spacecraft that revealed several areas bearing H2O-ice features. Independent telescopic observations showed a water exosphere of currently unknown origin. We explore the effects of meteoroid impacts on Ceres considering the topography obtained from the Dawn mission using a (Replaced: full-fledged replaced with: widely-used) micro-meteoroid model and ray-tracing techniques. Meteoroid populations with 0.01-2 mm diameters are considered. We analyze the short-term effects Ceres experiences during its current orbit as well as long-term effects over the entire precession cycle. We find the entire surface is subject to meteoroid bombardment leaving no areas in permanent shadow with respect to meteoroid influx. The equatorial parts of Ceres produce 80% more ejecta than the polar regions due to the large impact velocity of long-period comets. Mass flux, energy flux, and ejecta production vary seasonally by a factor of (Replaced: a few replaced with: 3–7) due to the inclined eccentric orbit. Compared to Mercury and the Moon, Ceres experiences significantly smaller effects of micro-meteoroid bombardment, with a total mass flux of 4.5±1.2×10(exp −17)kg m(exp −2)s(exp −1). On average Mercury is subjected to a 50× larger mass flux and generates 700× more ejecta than Ceres, while the lunar mass flux is 10× larger, and the ejecta generation is 30× larger than on Ceres. For these reasons, we find that meteoroid impacts are an unlikely candidate for the production of a water exosphere or significant excavation of surface features. The surface turnover rate from the micro-meteoroid populations considered is estimated to be 1.25 Myr on Ceres.

minor planets↗

Comment

An examination of ion concentration data from the AE-E, AE-C, and DE-2 spacecraft did not detect the small-comet influx into the upper atmosphere predicted by Frank et al. (1986). It is suggested that either the proposed cometary flux is overestimated by over an order of magnitude, or that the ionospheric signature used is not presently defined properly. In a reply, Frank et al. describe a more direct method for identifying the mechanisms participating in the interaction of the cometary water cloud with the ionosphere: examining DE-1 spacecraft images of the earth's UV afterglow for a crossing of a transient decrease, or atmospheric hole, with the DE-2 spacecraft, and verifying if the ionospheric signature identified with this crossing is noted at other times in the quiet atmosphere. A possible signature of the passage of the cometary water cloud through the ionosphere is identified, and a mode for this interaction is indicated.

Hanson, W. B.↗

Observations of thermal ion influxes about the space shuttle

Ion mass spectrometer measurements made as part of the University of Iowa's Plasma Diagnostic Package on the STS-3 and Spacelab 2 Space Shuttle missions sampled a variety of ion composition and collected ion current responses to gas emissions from the vehicle. The only other shuttle ion measurements were made by an Air Force Geophysics Laboratory (AFGL) quadrupole spectrometer flown on STS-4. Gas emissions change the distribution of the incoming plasma through scattering and charge transfer processes. A background flux of contaminant ion species (mostly relating to water) always exists in the near vicinity of the shuttle with a magnitude which is dependent on the look direction of the spectrometer but which varies differently with changes in the angle of attack than that of the ambient ions. There is a near shuttle wake cavity in the contaminant ion distributions which has a different spatial configuration than the wake of the ambient ions. Although water dumps produce the most persistent ion perturbations, the sources for ion current modification were best delineated from measurements made when only one or two of the Reaction Control System thrusters fired for a relatively long duration. Contaminant ion perturbations associated with such firings were observed to persist for the order of a second after the cessation of the firings. The dense thruster plumes are efficient collisional, charge exchange barriers to the passage of ambient ions. Collected ion current perturbations were more evident for firings of the rear verniers, whose plumes scatter off projecting surfaces, than for the nose thrusters. The effect of the Vernier firings was found to depend not only on the location and attitude of the spectrometer with respect to the shuttle and thruster plume direction, but also on the orientation of the local magnetic field with respect to the shuttle velocity.

Grebowsky, Joe M.↗

Idealized Large-Eddy Simulations of Stratocumulus Advecting over Cold Water. Part I: Boundary Layer Decoupling

Abstract We explore the decoupling physics of a stratocumulus-topped boundary layer (STBL) moving over cooler water, a situation mimicking warm-air advection (WADV). We simulate an initially well-mixed STBL over a doubly periodic domain with the sea surface temperature decreasing linearly over time using the System for Atmospheric Modeling large-eddy model. Due to the surface cooling, the STBL becomes increasingly stably stratified, manifested as a near-surface temperature inversion topped by a well-mixed cloud-containing layer. Unlike the stably stratified STBL in cold-air advection (CADV) that is characterized by cumulus coupling, the stratocumulus deck in the WADV is unambiguously decoupled from the sea surface, manifested as weakly negative buoyancy flux throughout the subcloud layer. Without the influxes of buoyancy from the surface, the convective circulation in the well-mixed cloud-containing layer is driven by cloud-top radiative cooling. In such a regime, the downdrafts propel the circulation, in contrast to that in CADV regime for which the cumulus updrafts play a more determinant role. Such a contrast in convection regime explains the difference in many aspects of the STBLs including the entrainment rate, cloud homogeneity, vertical exchanges of heat and moisture, and lifetime of the stratocumulus deck, with the last being subject to a more thorough investigation in Part II. Finally, we investigate under what conditions a secondary stratus near the surface (or fog) can form in the WADV. We found that weaker subsidence favors the formation of fog whereas a more rapid surface cooling rate does not. Significant Statement The low-lying blanketlike clouds, called stratocumulus (Sc), reflect much incoming sunlight, substantially modulating Earth’s temperature. While much is known about how the Sc evolves when it moves over warmer water, few studies examine the opposite situation of Sc moving over colder water. We used a high-resolution numerical model to simulate such a case. When moving over cold water, the Sc becomes unambiguously decoupled from the water surface, distinctive from its warm counterpart in which the Sc interacts with the water surface via intermittent cauliflower-like clouds called cumulus clouds. Such decoupling influences many aspects of the Sc–sea surface system, which combine to alter the ability of the Sc to reflect sunlight, thereby influencing the climate. This work laid the foundation for future work that quantifies the contribution of such a decoupled Sc regime to Earth’s radiative budget and climate change.

54 ENVIRONMENTAL SCIENCES↗

Techno-Economic Assessment for Opportunities to Integrate Algae Farming with Wastewater Treatment

This report investigates the economic and scalability potential for algal biomass production based on opportunities to couple algae farming with wastewater treatment (WWT). This activity was motivated in part by a recent influx of technology developers who are currently in various stages of planning, construction, and operation of algae facilities for treating municipal wastewater, all making claims of tremendous economic potential for algal WWT relative to other more traditional WWT methods when viewing treated wastewater as the primary product output and algal biomass as a secondary coproduct. In addition to solving for minimum biomass selling price (MBSP) for a farm configured to maximize biomass production while minimizing water footprint (when sourcing makeup water from local groundwater resources at added cost), the algal WWT cases evaluated here also solved for MBSP while assigning a treatment credit as a means to valorize the treated water as a coproduct in the farm model. This enables a consistent comparison against the National Renewable Energy Laboratory’s standard algae farm models.

09 BIOMASS FUELS↗

An Overview of Approaches and Challenges for Retrieving Marine Inherent Optical Properties from Ocean Color Remote Sensing

Ocean color measured from satellites provides daily global, synoptic views of spectral water-leaving reflectances that can be used to generate estimates of marine inherent optical properties (IOPs). These reflectances, namely the ratio of spectral upwelled radiances to spectral downwelled irradiances, describe the light exiting a water mass that defines its color. IOPs are the spectral absorption and scattering characteristics of ocean water and its dissolved and particulate constituents. Because of their dependence on the concentration and composition of marine constituents, IOPs can be used to describe the contents of the upper ocean mixed layer. This information is critical to further our scientific understanding of biogeochemical oceanic processes, such as organic carbon production and export, phytoplankton dynamics, and responses to climatic disturbances. Given their importance, the international ocean color community has invested significant effort in improving the quality of satellite-derived IOP products, both regionally and globally. Recognizing the current influx of data products into the community and the need to improve current algorithms in anticipation of new satellite instruments (e.g., the global, hyperspectral spectroradiometer of the NASA Plankton, Aerosol, Cloud, ocean Ecosystem (PACE) mission), we present a synopsis of the current state of the art in the retrieval of these core optical properties. Contemporary approaches for obtaining IOPs from satellite ocean color are reviewed and, for clarity, separated based their inversion methodology or the type of IOPs sought. Summaries of known uncertainties associated with each approach are provided, as well as common performance metrics used to evaluate them. We discuss current knowledge gaps and make recommendations for future investment for upcoming missions whose instrument characteristics diverge sufficiently from heritage and existing sensors to warrant reassessing current approaches.

Bio-optics↗

Model, Proxy and Isotopic Perspectives on the East African Humid Period

Both North and East Africa experienced more humid conditions during the early and mid-Holocene epoch (11,000-5000yr BP; 11-5 ka) relative to today. The North African Humid Period has been a major focus of paleoclimatic study, and represents a response of the hydrological cycle to the increase in boreal summer insolation and associated ocean, atmosphere and land surface feedbacks. Meanwhile, the mechanisms that caused the coeval East African Humid Period are poorly understood. Here, we use results from isotopeenabled coupled climate modeling experiments to investigate the cause of the East African Humid Period. The modeling results are interpreted alongside proxy records of both water balance and the isotopic composition of rainfall. Our simulations show that the orbitally-induced increase in dry season precipitation and the subsequent reduction in precipitation seasonality can explain the East African Humid Period, and this scenario agrees well with regional lake level and pollen paleoclimate data. Changes in zonal moisture flux from both the Atlantic and Indian Ocean account for the simulated increase in precipitation from June through November. Isotopic paleoclimate data and simulated changes in moisture source demonstrate that the western East African Rift Valley in particular experienced more humid conditions due to the influx of Atlantic moisture and enhanced convergence along the Congo Air Boundary. Our study demonstrates that zonal changes in moisture advection are an important determinant of climate variability in the East African region.

Tierney, Jessica E.↗

Observations of Subduction, Downward Heat Flux and Dense Filament Collapse in the Northern Gulf of Mexico

Submesoscale processes are important contributors to the global heat budget and generally support upward heat transport through restratification. However, in salinity‐stratified regions, such as the northern Gulf of Mexico with its influx of freshwater from the Mississippi‐Atchafalaya river system, temperature can act like a passive tracer and submesoscale processes can contribute to downward heat transport. Oceanic heat content is a factor in many environmental risks the region faces, for example, hurricane intensification, and marine heatwaves. During the 2022 field campaign of the Submesoscales Under Near‐Resonant Inertial Shear Experiment, a sampling plan was developed to study such submesoscale processes in high resolution. Over 31 hr, four assets (two research ships and two remotely controlled boats) drove in parallel across a dense filament, capturing its evolution in time and space. The observations show that surface waters, warmed by daytime solar radiation, were subducted and that the associated overturning circulation transported heat below the surface layer where it was later irreversibly mixed away. The estimated downward heat flux was as strong as the concurrent net air‐sea heat flux into the ocean. The filament was then observed to rapidly collapse which we attribute to boundary layer turbulence and the breakdown of geostrophic balance. The collapsing fronts display behaviors indicative of gravity currents. These observations highlight how in salinity‐stratified regions, frontal dynamics can be associated with downward heat flux and how the submesoscale can play an important role in the oceanic heat budget.

58 GEOSCIENCES↗

Hydrogen-isotope evidence for extrusion mechanisms of the Mount St Helens lava dome

Hydrogen isotope analyses were used to determine water content and deuterium content for 18 samples of the Mount St Helens dome dacite in an attempt to identify the triggering mechanisms for periodic dome-building eruptions of lava. These isotope data, the first ever collected from an active lava dome, suggest a steady-state process of magma evolution combining crystallization-induced volatile production in the chamber with three different degassing mechanisms: closed-system volatile loss in the magma chamber, open-system volatile release during ascent, and kinetically controlled degassing upon eruption at the surface. The data suggest the future dome-building eruptions may require a new influx of volatile-rich magma into the chamber.

Anderson, Steven W.↗

The Unique Capabilities of the Global Hawk Aircraft for the Study of Climate Changes

Due to unprecedented extent and flexibility of the coverage that is now attainable both in space and time, stratospheric unmanned aircraft, such as the Global Hawk (GH), offers new opportunities for the study of climate changes. The capability of performing long flights at altitudes close to the boundary conditions of radiative processes, and of following the diurnal variation of chemical species and clouds, make the GH competitive with LEO and geosynchronous satellites, and even capable of new observations that are not possible from satellites. This paper discusses how the GH can be used to make relevant advancements in most of the issues that are related to climate change studies, such as: Earth Radiation Budget, Water Cycle, Ecosystems and Upper Troposphere-Lower Stratosphere, as well as to the monitoring and control of Greenhouse Gases and Air Quality . Collaboration between NASA and Italian scientific institutions, within the framework of the US.-Italy Cooperation on Climate Change, is providing the opportunity to rapidly deploy new instruments on the GH and to possibly operate the aircraft from an Italian site in the Mediterranean area. From this area, which is considered highly vulnerable to climate change, meridional transects would allow the crossing of Polar and Sub Tropical Jets, as well as a complete crossing of the Inter Tropical Convergence Zone, while latitudinal ones would follow the influx from Asia and North America. Regions otherwise difficult to access, such as Central Africa and the Tibetan Plateau, could be reached and better investigated. An overview of these new opportunities will be given and discussed.

Cairo, F.↗

Photochemistry of Saturn's Atmosphere: Hydrocarbon Chemistry and Comparisons with ISO Observations - 1

To investigate the details of hydrocarbon photochemistry on Saturn, we have developed a one-dimensional diurnally averaged model that couples hydrocarbon and oxygen photochemistry, molecular and eddy diffusion, radiative transfer, and condensation. The model results are compared with observations from the Infrared Space Observatory (ISO) to place tighter constraints on molecular abundances, to better define Saturn's eddy diffusion coefficient profile, and to identify important chemical schemes that control the abundances of the observable hydrocarbons in Saturn's upper atmosphere. From the ISO observations, we determine that the column 12 densities of CH3, CH3C2H, and C4H2 above 10 mbar are 4 (sup +2) (sub -1.5) x 10 (exp 13) cm (sup -2), (1.1 plus or minus 0.3) x 10 (exp 15) cm (exp -2), and (1.2 plus or minus 0.3) x 10 (exp 14) cm (sup -2), respectively. The observed ISO emission features also indicate C2H2 mixing ratios of 1.2 (sup +0.9) (sub -0.6) x 10 (exp -6) at 0.3 mbar and (2.7 plus or minus 0.8) x 10 (exp -7) at 1.4 mbar, and a C2H6 mixing ratio of (9 plus or minus 2.5) x 10 (exp -6) at 0.5 mbar. Upper limits are provided for C2H4, CH2CCH2, C3H8, and C6H2 sensitivity of the model results to variations in the eddy diffusion coefficient profile, the solar flux, the CH4 photolysis branching ratios, the atomic hydrogen influx, and key reaction rates are discussed in detail. We find that C4H2 and CH3C2H are particularly good tracers of important chemical processes and physical conditions in Saturn's upper atmosphere, and C2H6 is a good tracer of the eddy diffusion coefficient in Saturn's lower stratosphere. The eddy diffusion coefficient must be smaller than approximately 3 x 10 (exp 4) sq cm s (sup -1) at pressures greater than 1 mbar in order to reproduce the C2H6 abundance inferred from ISO observations. The eddy diffusion coefficients in the upper stratosphere could be constrained by observations of CH3 radicals if the low-temperature chemistry of CH3 were better understood. We also discuss the implications of our modeling for aerosol formation in Saturn's lower stratosphere-diacetylene, butane, and water condense between approximately 1 and 300 mbar in our model and will dominate stratospheric haze formation at nonauroral latitudes. Our photochemical models will be useful for planning observational sequences and for analyzing data from the upcoming Cassini mission.

Moses, Julianne I.↗