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FY24 Task 5: Leachate Disposition

Directly feeding sludge solids to the high-level waste (HLW) Waste Treatment Plant represents an alternative flowsheet seeking to initiate sludge processing as soon as possible. Key processing functions previously captured during baseline pretreatment operations include leaching and washing prior to solids concentration. These operations should be considered in the potential direct feed flowsheets to maximize waste feed loading, minimize HLW volume, and mitigate corrosion challenges associated with vitrification of high phosphate and fluoride concentrations. Additionally, single-shell tank (SST) retrievals and waste transfers to double-shell tanks (DSTs) in a direct feed flowsheet would likely also benefit from some level of leaching, washing, and solids concentration in order to reduce DST space and mission duration. These operations could occur in a new facility or potentially in available DSTs. If washing and leaching are utilized, an effective disposition pathway for the wash water and leachate solutions are needed. Three target species that benefit significantly from leaching and washing are phosphate, fluoride and aluminum. Phosphate (PO 4 3- ) and fluoride (F - ) can contribute substantially to the amount of carrier fluid needed for dissolution, and the resulting volume of liquid generated. Disposition of this retrieval solution should be evaluated in order to prevent crystallization of these anions throughout system processing. Since there is a high probability that any retrieval solutions will be at or near their PO 4 3- and F - solubility limits, evaporation or blending with a high Na supernate (>3.5 M) is not recommended for the wash water streams without a method to remove precipitants prior to solution disposal. Additionally, aluminum present in the southeast quadrant of the Hanford site represents roughly 60% of the waste solids in the initial processing tanks. These aluminum solids are in the form of gibbsite (Al(OH) 3 ) and can pose significant challenges for processing due to the fast-settling times and high solids loading associated with these materials. Easily remediated by caustic addition to the solids, these wash solutions could be processed through crystalline silicotitanate (CST) ion exchange columns to prepare the supernate solutions for disposition. The current target for feed conditions to the Low Activity Waste (LAW) melter are waste streams that contain nominally 5-6 M Na. Fractions within the tanks contain upwards of 0.2 M phosphate and fluoride in solution at 3.5 M Na. Concentrating these solutions above 5 M Na would result in an exceedance of the solubility limits, and potential for uncontrolled precipitation of the phosphate and fluoride crystal material. The resulting crystalline salt material is typically sodium fluoride phosphate, also referred to as natrophosphate (Na 7 FPO 4 ·19H 2 O). Salt phases are of importance in tank waste due to their chemical reactivity, which can result in precipitation, dissolution, or transformation, impacting any downstream processes (Bolling et al. 2020, Russell, Snow, and Peterson 2010). Salt generation and precipitation could pose challenges by causing system plugging and melter corrosion if left in the supernate stream, or limit sodium molarity of the supernate that would be accepted without incident in waste operations. To understand the impact of this salt generation, the crystallization of natrophosphate in multiple simulant feed matrices was studied to understand the implications of various tank waste supernate chemistries. Three matrices were examined: high PO 4 3- /low F - , low PO 4 3- /high F - , and an average matrix. Subsequent testing was performed with the average matrix with the inclusion of CsNO 3 , and a final run with the average matrix including CsNO 3 and a 137 Cs spike for tracer purposes.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

A double peak in the seasonality of California's photosynthesis as observed from space

Solar-induced chlorophyll fluorescence (SIF) has been shown to be a powerful proxy for photosynthesis and gross primary productivity (GPP). The recently launched TROPOspheric Monitoring Instrument (TROPOMI) features the required spectral resolution and signal-to-noise ratio to retrieve SIF from space. Here, we present a downscaling method to obtain 500 m spatial resolution SIF over California. We report daily values based on a 14 d window. TROPOMI SIF data show a strong correspondence with daily GPP estimates at AmeriFlux sites across multiple ecosystems in California. We find a linear relationship between SIF and GPP that is largely invariant across ecosystems with an intercept that is not significantly different from zero. Measurements of SIF from TROPOMI agree with MODerate Resolution Imaging Spectroradiometer (MODIS) vegetation indices – the normalized difference vegetation index (NDVI), enhanced vegetation index (EVI), and near-infrared reflectance of vegetation index (NIR$_v$) – at annual timescales but indicate different temporal dynamics at monthly and daily timescales. TROPOMI SIF data show a double peak in the seasonality of photosynthesis, a feature that is not present in the MODIS vegetation indices. The different seasonality in the vegetation indices may be due to a clear-sky bias in the vegetation indices, whereas previous work has shown SIF to have a low sensitivity to clouds and to detect the downregulation of photosynthesis even when plants appear green. We further decompose the spatiotemporal patterns in the SIF data based on land cover. The double peak in the seasonality of California's photosynthesis is due to two processes that are out of phase: grasses, chaparral, and oak savanna ecosystems show an April maximum, while evergreen forests peak in June. An empirical orthogonal function (EOF) analysis corroborates the phase offset and spatial patterns driving the double peak. The EOF analysis further indicates that two spatiotemporal patterns explain 84 % of the variability in the SIF data. Results shown here are promising for obtaining global GPP at sub-kilometer spatial scales and identifying the processes driving carbon uptake.

54 ENVIRONMENTAL SCIENCES↗

Observing Ice in Clouds from Space

There are many satellite observations of cloud top properties and the liquid and rain content of clouds, however, we do not yet quantitatively understand the processes that control the water budget of the upper troposphere where ice is the predominant phase, and how these processes are linked to precipitation processes and the radiative energy budget. The ice in clouds in the upper troposphere either melts into rain or is detrained, and persists, as cirrus clouds affecting the hydrological and energy cycle, respectively. Fully modeling the Earth's climate and improving weather and climate forecasts requires accurate satellite measurements of various cloud properties at the temporal and spatial scales of cloud processes. These properties include cloud horizontal and vertical structure, cloud water content and some measure of particle sizes and shapes. The uncertainty in knowledge of these ice characteristics is reflected in the large discrepancies in model simulations of the upper tropospheric water budget. Model simulations are sensitive to the partition of ice between precipitation and outflow processes, i.e., to the parameterization of ice clouds and ice processes. One barrier to achieving accurate global ice cloud properties is the lack of adequate observations at millimeter and submillimeter wavelengths (183-874 GHz). Recent advances in instrumentation have allowed for the development and implementation of an airborne submillimeter-wave radiometer. The brightness temperatures at these frequencies are especially sensitive to cirrus ice particle sizes (because they are comparable to the wavelength). This allows for more accurate ice water path estimates when multiple channels are used to probe into the cloud layers. Further, submillimeter wavelengths offer simplicity in the retrieval algorithms because they do not probe into the liquid and near surface portions of clouds, thus requiring only one term of the radiative transfer equation (ice scattering) to relate brightness temperatures to ice. The next step is a satellite mission designed to acquire global Earth radiance measurements in the submillimeter-wave region, thus bridging the measurement gap between microwave sounders and shorter-wavelength infrared and visible sensors. This presentation provides scientific justification and an approach to measuring ice water path and particle size from a satellite platform that spans a range encompassing both the hydrologically active and radiatively active components of cloud systems.

Ackerman, S.↗

X-Ray Computed Tomography: The First Step in Mars Sample Return Processing

The Mars 2020 rover mission will collect and cache samples from the martian surface for possible retrieval and subsequent return to Earth. If the samples are returned, that mission would likely present an opportunity to analyze returned Mars samples within a geologic context on Mars. In addition, it may provide definitive information about the existence of past or present life on Mars. Mars sample return presents unique challenges for the collection, containment, transport, curation and processing of samples [1] Foremost in the processing of returned samples are the closely paired considerations of life detection and Planetary Protection. In order to achieve Mars Sample Return (MSR) science goals, reliable analyses will depend on overcoming some challenging signal/noise-related issues where sparse martian organic compounds must be reliably analyzed against the contamination background. While reliable analyses will depend on initial clean acquisition and robust documentation of all aspects of developing and managing the cache [2], there needs to be a reliable sample handling and analysis procedure that accounts for a variety of materials which may or may not contain evidence of past or present martian life. A recent report [3] suggests that a defined set of measurements should be made to effectively inform both science and Planetary Protection, when applied in the context of the two competing null hypotheses: 1) that there is no detectable life in the samples; or 2) that there is martian life in the samples. The defined measurements would include a phased approach that would be accepted by the community to preserve the bulk of the material, but provide unambiguous science data that can be used and interpreted by various disciplines. Fore-most is the concern that the initial steps would ensure the pristine nature of the samples. Preliminary, non-invasive techniques such as computed X-ray tomography (XCT) have been suggested as the first method to interrogate and characterize the cached samples without altering the materials [1,2]. A recent report [4] indicates that XCT may minimally alter samples for some techniques, and work is needed to quantify these effects, maximizing science return from XCT initial analysis while minimizing effects.

Welzenbach, L. C.↗

Convective and Stratiform Precipitation Processes and their Relationship to Latent Heating

The global hydrological cycle is central to the Earth's climate system, with rainfall and the physics of its formation acting as the key links in the cycle. Two-thirds of global rainfall occurs in the Tropics. Associated with this rainfall is a vast amount of heat, which is known as latent heat. It arises mainly due to the phase change of water vapor condensing into liquid droplets; three-fourths of the total heat energy available to the Earth's atmosphere comes from tropical rainfall. In addition, fresh water provided by tropical rainfall and its variability exerts a large impact upon the structure and motions of the upper ocean layer. An improved convective -stratiform heating (CSH) algorithm has been developed to obtain the 3D structure of cloud heating over the Tropics based on two sources of information: 1) rainfall information, namely its amount and the fraction due to light rain intensity, observed directly from the Precipitation Radar (PR) on board the TRMM satellite and 2) synthetic cloud physics information obtained from cloud-resolving model (CRM) simulations of cloud systems. The cloud simulations provide details on cloud processes, specifically latent heating, eddy heat flux convergence and radiative heating/cooling, that. are not directly observable by satellite. The new CSH algorithm-derived heating has a noticeably different heating structure over both ocean and land regions compared to the previous CSH algorithm. One of the major differences between new and old algorithms is that the level of maximum cloud heating occurs 1 to 1.5 km lower in the atmosphere in the new algorithm. This can effect the structure of the implied air currents associated with the general circulation of the atmosphere in the Tropics. The new CSH algorithm will be used provide retrieved heating data to other heating algorithms to supplement their performance.

Tao, Wei-Kuo↗

The Komplast Experiment: Space Environmental Effects after 12 Years in LEO (and Counting)

The Komplast materials experiment was designed by the Khrunichev State Research and Production Space Center, together with other Russian scientific institutes, and has been carried out by Mission Control Moscow since 18. Komplast panels fitted with material samples and sensors were located on the International Space Station (ISS) Functional Cargo Block (FGB) module exterior surface. Within the framework of this experiment, the purpose was to study the effect of the low earth orbit (LEO) environment on exposed samples of various materials. The panels were sent into orbit with the FGB when it launched on November 20, 1998. Panels #2 and #10 were retrieved during Russian extravehicular activity in February 2011 and sealed within cases to temporarily protect the samples from exposure to air until they could be studied on the ground. Panel #2 contained an experiment to detect micrometeoroid and orbital debris (MMOD) impacts, radiation and UV sensors, several pieces of electrical cable, and samples made from elastomeric and fluoroplastic materials. Panel #10 contained a temperature sensor, and both carbon composite and adhesive-bonded samples. A figure shows the location of panels #2 and #10 on the FGB module aft endcone. The panels were subsequently returned to Earth by Space Shuttle Discovery on the STS-133/ULF-5 mission after 12 years of LEO exposure and opened in an argon chamber at the Institute of Nuclear Physics at Moscow State University in July 2011. Based on the results of analyzing the readings from sensors located on Komplast panels and in studying material samples from the panels, the comprehensive effect of spaceflight factors on the FGB (at the locations of Panels #2 and #10) was evaluated. Total solar exposure was determined to be 960 +/- 200 kJ/square cm or 21,000 equivalent solar hours. Because of location of these two panels and the ISS flight attitude, atomic oxygen (AO) fluence was relatively low for such a long duration exposure, approximately 1.5x10 (exp 21) O atoms/sq. cm. Most of the AO fluence occurred during the early phase of ISS assembly. Temperatures ranged from a maximum of 107 C to a minimum of -80 C. The MMOD environment was determined, as is shown. Interestingly, the distribution of craters and low-velocity impact particles observed in the 5-50 micron size range was approx 2-3 orders of magnitude higher than that predicted by the ORDEM2000 model of natural and artificial origin microparticles in the ISS orbit. Contamination observations were also made, through the evaluation of optical properties on thermal control coatings and by the examination of visible deposits located near several samples on the panels, primarily from elastomeric samples. These elastomer samples were extensively investigated for their physical property changes and sealing capability. In addition, 16 samples of adhesive-bonded joints using three types of epoxy adhesive were evaluated studying fracture toughness, failure surface, and adhesive volume properties. Both rubber and adhesive-bonded specimens also underwent additional (post-flight) ground-based exposures to simulate a total 30 years in LEO prior to their evaluation. Overall, results indicate that space environmental effects will not adversely impact the service life of the FGB through 2028. Our investigation is complete and a summary of the results obtained from this uniquely long-duration exposure experiment will be presented.

Shaevich, S. K.↗

Biomass burning emission analysis based on MODIS aerosol optical depth and AeroCom multi-model simulations: implications for model constraints and emission inventories

We assessed the biomass burning (BB) smoke aerosol optical depth (AOD) simulations of 11 global models that participated in the AeroCom phase III BB emission experiment. By comparing multi-model simulations and satellite observations in the vicinity of fires over 13 regions globally, we (1) assess model-simulated BB AOD performance as an indication of smoke source–strength, (2) identify regions where the common emission dataset used by the models might underestimate or overestimate smoke sources, and (3) assess model diversity and identify underlying causes as much as possible. Using satellite-derived AOD snapshots to constrain source strength works best where BB smoke from active sources dominates background non-BB aerosol, such as in boreal forest regions and over South America and southern hemispheric Africa. The comparison is inconclusive where the total AOD is low, as in many agricultural burning areas, and where the background is high, such as parts of India and China. Many inter-model BB AOD differences can be traced to differences in values for the mass ratio of organic aerosol to organic carbon, the BB aerosol mass extinction efficiency, and the aerosol loss rate from each model. The results point to a need for increased numbers of available BB cases for study in some regions and especially to a need for more extensive regional-to-global-scale measurements of aerosol loss rates and of detailed particle microphysical and optical properties; this would both better constrain models and help distinguish BB from other aerosol types in satellite retrievals. More generally, there is the need for additional efforts at constraining aerosol source strength and other model attributes with multi-platform observations.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

ACE-Asia Aerosol Optical Depth and Water Vapor Measured by Airborne Sunphotometers and Related to Other Measurements and Calculations

In the Spring 2001 phase of the Asian Pacific Regional Aerosol Characterization Experiment (ACE-Asia), the 6-channel NASA Ames Airborne Tracking Sunphotometer (AATS-6) operated on 15 of the 19 research flights of the NCAR C-130, while its 14-channel counterpart (AATS- 14) flew successfully on all 18 research flights of the CIRPAS Twin Otter. ACE-Asia studied aerosol outflow from the Asian continent to the Pacific basin. It was designed to integrate suborbital and satellite measurements and models so as to reduce the uncertainty in calculations of the climate forcing due to aerosols. AATS-6 and AATS-14 measured solar beam transmission at 6 and 14 wavelengths (380-1021 and 354-1558 nm, respectively), yielding aerosol optical depth (AOD) spectra and column water vapor (CWV). Vertical differentiation in profiles yielded aerosol extinction spectra and water vapor concentration. The wavelength dependence of these AOD and extinction spectra indicates that supermicron dust was often a major component of the ACE-Asia aerosol. Frequently this dust-containing aerosol extended to high altitudes. For example, in AATS- 14 profiles analyzed to date, 36% of full-column AOD at 525 nm was above 3 km. In contrast, only 10% of CWV was above 3 km. Analyses and applications of AATS-6 and AATS-14 data to date include comparisons to (i) extinction products derived using in situ measurements, (ii) extinction profiles derived from lidar measurements, and (iii) AOD retrievals from the Multi-angle Imaging Spectro-Radiometer (MISR) aboard the TERRA satellite. Other planned collaborative studies include comparisons to results from size spectrometers, chemical measurements, other satellite sensors, flux radiometers, and chemical transport models. Early results of these studies will be presented.

Livingston, John M.↗

Dust, Pollution, and Biomass Burning Aerosols in Asian Pacific: A Column Surface/Satellite Perspective

Many recent field experiments are designed to study the compelling variability in spatial and temporal scale of both pollution-derived and naturally occurring aerosols, which often exist in high concentrations over eastern/southeastern Asia and along the rim of the western Pacific. For example, the phase-I of ACE-Asia was conducted from March-May 2001 in the vicinity of the Gobi desert, East Coast of China, Yellow Sea, Korea, and Japan, along the pathway of Kosa (severe events that blanket East Asia with yellow desert dust, peaked in the Spring season). Asian dust typically originates in desert areas far from polluted urban regions. During transport, dust layers can interact with anthropogenic sulfate and soot aerosols from heavily polluted urban areas. Springtime is also the peak season for biomass burning in southeastern Asia. Added to the complex effects of clouds and natural marine aerosols, dust particles reaching the marine environment can have drastically different properties than those from the source. Thus, understanding the unique temporal and spatial variations of Asian aerosols is of special importance in regional-to-global climate issues such as radiative forcing, the hydrological cycle, and primary biological productivity in the mid-Pacific Ocean. During ACE-Asia we have measured continuously aerosol physical/optical/radiative properties, column precipitable water amount, and surface reflectivity over homogeneous areas from surface. The inclusion of flux measurements permits the determination of aerosol radiative flux in addition to measurements of loading and optical depth. At the time of the Terra/MODIS (Moderate Resolution Imaging Spectroradiometer), SeaWiFS (Sea-viewing Wide Field-of-view Sensor), TOMS (Total Ozone Mapping Spectrometer) and other satellite overpasses, these ground-based observations can provide valuable data to compare with satellite retrievals over land. A column satellite-surface perspective of Asian aerosols will be presented and will discuss their implications in regional-to-global effects on climate, fresh water redistribution, and health issues. (to be presented in Hawaii, April 28 - May 3, and Beijing, China, May 6 - 10, 2002)

Tsay, Si-Chee↗

Validation of SMAP Surface Soil Moisture Products with Core Validation Sites

The NASA Soil Moisture Active Passive (SMAP) mission has utilized a set of core validation sites as the primary methodology in assessing the soil moisture retrieval algorithm performance. Those sites provide well calibrated in situ soil moisture measurements within SMAP product grid pixels for diverse conditions and locations.The estimation of the average soil moisture within the SMAP product grid pixels based on in situ measurements is more reliable when location specific calibration of the sensors has been performed and there is adequate replication over the spatial domain, with an up-scaling function based on analysis using independent estimates of the soil moisture distribution. SMAP fulfilled these requirements through a collaborative CalVal Partner program.This paper presents the results from 34 candidate core validation sites for the first eleven months of the SMAP mission. As a result of the screening of the sites prior to the availability of SMAP data, out of the 34 candidate sites 18 sites fulfilled all the requirements at one of the resolution scales (at least). The rest of the sites are used as secondary information in algorithm evaluation. The results indicate that the SMAP radiometer-based soil moisture data product meets its expected performance of 0.04 cu m/cu m volumetric soil moisture (unbiased root mean square error); the combined radar-radiometer product is close to its expected performance of 0.04 cu m/cu m, and the radar-based product meets its target accuracy of 0.06 cu m/cu m (the lengths of the combined and radar-based products are truncated to about 10 weeks because of the SMAP radar failure). Upon completing the intensive CalVal phase of the mission the SMAP project will continue to enhance the products in the primary and extended geographic domains, in co-operation with the CalVal Partners, by continuing the comparisons over the existing core validation sites and inclusion of candidate sites that can address shortcomings.

SMAP↗

Australian wildfire smoke in the stratosphere: the decay phase in 2020/2021 and impact on ozone depletion

Abstract. Record-breaking wildfires raged in southeastern Australia in late December 2019 and early January 2020. Rather strong pyrocumulonimbus (pyroCb) convection developed over the fire areas and lofted enormous amounts of biomass burning smoke into the tropopause region and caused the strongest wildfire-related stratospheric aerosol perturbation ever observed around the globe. We discuss the geometrical, optical, and microphysical properties of the stratospheric smoke layers and the decay of this major stratospheric perturbation. A multiwavelength polarization Raman lidar at Punta Arenas (53.2∘ S, 70.9∘ W), southern Chile, and an elastic backscatter Raman lidar at Río Grande (53.8∘ S, 67.7∘ W) in southern Argentina, were operated to monitor the major record-breaking event until the end of 2021. These lidar measurements can be regarded as representative for mid to high latitudes in the Southern Hemisphere. A unique dynamical feature, an anticyclonic, smoke-filled vortex with 1000 km horizontal width and 5 km vertical extent, which ascended by about 500 m d−1, was observed over the full last week of January 2020. The key results of the long-term study are as follows. The smoke layers extended, on average, from 9 to 24 km in height. The smoke partly ascended to more than 30 km height as a result of self-lofting processes. Clear signs of a smoke impact on the record-breaking ozone hole over Antarctica in September–November 2020 were found. A slow decay of the stratospheric perturbation detected by means of the 532 nm aerosol optical thickness (AOT) yielded an e-folding decay time of 19–20 months. The maximum smoke AOT was around 1.0 over Punta Arenas in January 2020 and thus 2 to 3 orders of magnitude above the stratospheric aerosol background of 0.005. After 2 months with strongly varying smoke conditions, the 532 nm AOT decreased to 0.03-0.06 from March–December 2020 and to 0.015–0.03 throughout 2021. The particle extinction coefficients at 532 nm were in the range of 10–75 Mm−1 in January 2020 and, later on, mostly between 1 and 5 Mm−1. Combined lidar–photometer retrievals revealed typical smoke extinction-to-backscatter ratios of 69 ± 19 sr (at 355 nm), 91 ± 17 sr (at 532 nm), and 120 ± 22 sr (at 1064 nm). An ozone reduction of 20 %–25 % in the 15–22 km height range was observed over Antarctica and New Zealand ozonesonde stations in the smoke-polluted air, with particle surface area concentrations of 1–5 µm2 cm−3.

Ohneiser, Kevin↗

166 GHz Ice Scattering Signal in Cold-Season Precipitating Cloud Systems

Surface snowfall can be produced by a variety of forcing mechanisms that are accompanied by different in-cloud physical processes and microphysical composition. For instance, shallow cumuliform snowfall forced by marine cold air outbreaks shows distinct geographic and seasonal signatures and plays in important role in annual snowfall production in many regions worldwide. Coincident CloudSat-CALIPSO observations confirm that oceanic regions exhibiting frequent shallow cumuliform snow are typically composed of mixed-phase cloud and precipitation particles and display passive microwave brightness temperature behavior that is dominated by cloud liquid water emission, while combined Global Precipitation Measurement (GPM) radiometer and surface radar studies of intense shallow cumuliform events indicate significant ice particle scattering signals at the highest GPM radiometer frequencies. Passive microwave imager channels in the 37 to 89 GHz range have long been used to detect precipitation-sized ice particle scattering signatures in clouds. Dual polarization plays an important role in distinguishing between scattering signatures and other background variability. The GPM Microwave Imager (GMI) is the first satellite radiometer to possess dual-polarized channels at 166 GHz. These high-frequency channels are more susceptible to emission and attenuation by cloud liquid water and water vapor than lower-frequency channels, but are also more sensitive to ice scattering. This research studies the ice scattering information contained in the 166 GHz channels compared to the historically used 85/89 GHz channels on previous sensors. A 166 GHz scattering index (SI) will be developed to understand how its correlation with non-precipitating ice scattering at higher altitudes also affects the 166 GHz scattering signature in cold-season precipitating cloud systems. The 166 GHz SI will be used to possibly isolate precipitation scattering signature for different snowfall modes (shallow convective vs. deep stratiform). The supercooled liquid water affecting shallow convective systems and drastically reducing the scattering signal could be detected and quantified, providing additional information for convective snow detection and quantification in solid precipitation retrieval algorithms.

Lisa Milani↗

Determining the Solubility Behavior of Kogarkoite in Simulated Nuclear Waste

Kogarkoite (Na 3 FSO 4 ) is a sparingly soluble fluoride–sulfate double salt that has been identified in high level nuclear waste sludge at the Hanford Site and, more recently, in sludge batch compilation samples at the Savannah River Site (SRS). Due to its complex dissolution behavior, which exhibits an inverse dependence on sodium ion activity, the presence of this mineral poses significant challenges to waste retrieval and processing. Incomplete dissolution during sludge washing can lead to the retention of fluoride and sulfate in the high-level waste feed, potentially causing the formation of corrosive, immiscible molten salt layers, known as "glass gall,” in vitrification melters. Current efforts to optimize flowsheet parameters and wash-water volumes are hindered by the absence of a commercially available, certified reference material, which prevents the accurate calibration of analytical methods and the verification of dissolution kinetics. To address this critical gap, this research focuses on the laboratory synthesis of pure Kogarkoite to serve as a standard for comprehensive solubility and washing performance testing. A coupled synthesis and simulant campaign was executed using an evaporative crystallization protocol designed to replicate the dynamic concentration effects observed in tank farm operations. Thirteen simulant matrices were prepared by dissolving systematically varied ratios of sodium fluoride (NaF) and sodium sulfate (Na 2 SO 4 ) in deionized water under three distinct caustic regimes: 0.0 g (control), 4.0 g (~1 M), and 12.0 g (~3 M) sodium hydroxide (NaOH). While thermodynamic equilibrium models suggest that high-caustic environments should favor the stability of the double salt7, results from this evaporative study at 25 0 C revealed a distinct kinetic divergence. Simulants with high hydroxide loading predominantly yielded large, blocky crystals of sodium sulfate decahydrate (Na 2 SO 4 .10H 2 O). Successful synthesis of pure Kogarkoite was achieved exclusively in specific NaOH-free compositional windows, where the precipitate manifested as fine, opaque granular aggregates. Ion chromatography (IC) analysis confirmed phase purity through the simultaneous stoichiometric depletion of both fluoride and sulfate from the supernatant. This successful synthesis establishes a reproducible route to generate bulk Kogarkoite, enabling the subsequent phase of quantitative dissolution testing using inhibited water to optimize sludge-batch assembly.

Sarker, Md Sharif [Florida International Univ. (FI↗

A Study of Direct and Cloud-Mediated Radiative Forcing of Climate Due to Aerosols

The Intergovernmental Panel on Climate Change (IPCC) has reported that in the southeastern US and eastern China, the general greenhouse warming due to anthropogenic gaseous emissions is dominated by the cooling effect of anthropogenic aerosols. To verify this model prediction in eastern China and southeastern US, we analyzed regional patterns of climate changes at 72 stations in eastern China during 1951- 94 (44 years), and at 52 stations in the southeastern US during 1949-94 (46 years) to detect the fingerprint of aerosol radiative forcing. It was found that the mean rates of change of annual mean daily, maximum, minimum temperatures and diurnal temperature range (DTR) in eastern China were 0.8, -0.2, 1.8, and -2.0 C/100 years respectively, while the mean rates of change of annual mean daily, maximum, minimum temperatures and DTR in the southeastern US were -0.2, -0.6, 0.2, and -0.8 C/100 years, respectively. This indicates that the high rate of increase in annual mean minimum temperature in eastern China results in a slightly warming trend of daily temperature, while the high rate of decrease in annual mean maximum temperature and low rate of increase in annual mean minimum temperature lead to the cooling trend of daily temperature in the southeastern US. We found that the warming from the longwave forcing due to both greenhouse gases and aerosols was completely counteracted by the shortwave aerosol forcing in the southeastern US in the past 46 years. A slightly overall warming trend in eastern China is evident; winters have become milder. This finding is explained by hypothesizing that increasing energy usage during the past 44 years has resulted in more coal and biomass burning, thus increasing the emission of absorbing soot and organic aerosols in eastern China. Such emissions, in addition to well-known Asia dust and greenhouse gases, may be responsible for the winter warming trend in eastern China that we have reported here. The sensitivity of aerosol radiative properties to aerosol composition, size distribution, relative humidity (RH) is examined for the following aerosol systems: inorganic and organic ions (Cl-, Br-, NO3 -, SO4 2-, Na+, NH4 +, K+, Ca2+, Mg2+, HCOO-, CH3COO-, CH3CH2COO-, CH3COCOO-, OOCCOO2-, MSA-1); water-insoluble inorganic and organic compounds (elemental carbon, n-alkanes, SiO2, Al2O3, Fe2O3 and other organic compounds). The partial molar refraction method was used to calculate the real part of the refractive index. It was found that the asymmetry factor increased by approximately 48% with the real part varying from 1.40 to 1.65, and the single scattering albedo decreased by 24% with the imaginary part varying from -0.005 to -0.1. The asymmetry factor increased by 5.4 times with the geometric standard deviation varying from 1.2 to 3.0. The radiation transmission is very sensitive to the change in size distribution; other factors are not as significant. To determine the aerosol direct radiative forcing (ADRF), the aerosol optical depth (AOD) values at the three operational wavelengths (415, 500 and 673 nm) were determined at a regionally representative site, namely, Mt. Gibbs (35.78 deg N, 82.29 deg W, elevation 2006 m) in Mt. Mitchell State Park, NC, and a site located in an adjacent valley (Black Mountain, 35.66 deg N, 82.38 deg W, elevation 951 m) in the southeastern US. The two sites are separated horizontally by 10 km and vertically by 1 km. It was found that the representative total AOD values at 500 nm at the valley site for highly polluted (HP), marine (M) and continental (C) air masses were 0.68 +/- 0.33, 0.29 +/- 0.19 and 0.10 +/- 0.04, respectively. A search-graph method was used to retrieve the columnar size distribution (number concentration N, effective radius reff and geometric standard deviation=?g) from the optical depth observations at three operational wavelengths. The ground albedo, single scattering albedo and imaginary part of the refractive index were calculated using a mathematically unique procedure involving a Mie code and a radiative transfer code in conjunction with the retrieved aerosol size distribution, AOD, and diffuse-direct irradiance ratio. It was found that N, r(eff) and sigma(g) were in the ranges of 10 to 1.7 x 10(exp 4)/cubic cm, 0.09 to 0.68 micrometers and 1.12 to 2.95, respectively. The asymmetry factor and single scattering albedo were in the ranges of 0.63 to 0.75 and 0.74 to 0.97 respectively. The ground albedo for the forested terrain and imaginary part of refractive index were found to be in the ranges of 0.06 to 0.29 and 0.005 to 0.051 respectively. On the basis of these aerosol radiative properties obtained at the research sites and computations using the Column Radiation Model (CRM) of National Center of Atmospheric Research (NCAR) Community Climate Model (CCM3), it was found that the average cloud-free 24-hour ADRF values were -13 +/- 8, -8 +/- 3, -33 +/- 16 W/square m for marine, continental, and polluted air masses, respectively. On the assumption that the fractional coverage of clouds is 0.61, it was estimated that the annual mean ADRF was 7 +/- 2 W/square m in the southeastern US. The review with respect to the current knowledge of organic acids shows that aerosol formate and acetate concentrations range from 0.02 to 5.3 nmol/cubic m and from 0.03 to 12.4 nmol/cubic m respectively, and that between 34% to 77% of formate and between 21% to 66% of acetate are present in the fine fraction of aerosols. It was found that although most (98-99%) of these volatile organic acids were present in the gas phase, their concentrations in the aerosol particles were sufficient to make them a good candidate for cloud condensation nuclei (CCN). It is hypothesized that organic acids are at least one of the primary sources of CCN in the atmosphere due to their ubiquitous presence in the troposphere, especially over the continental forested areas. The results of our measurements at Palmer Station, Antarctica show that the daily average CCN concentrations at 0.3% and 1% supersaturations ranged from 0.3 to 160/cubic cm and from 4 to 168/cubic cm, respectively, during the period from 17 January to 26 February, 1994. New evidence for substantial and definitive CCN enhancement near and within cloud has been observed at Mt. Mitchell, North Carolina. The results show that the average monthly CCN concentrations were 460 +/- 217, 386 +/- 286, 429 +/- 228 and 238 +/- 134/cubic cm for in-cloud, overcast, clear and rainy conditions, respectively. The typical CCN spectra show that there were a lot of small CCN produced and the ion concentrations (especially H+ and SO4 2-) were very high during the CCN enhancement period. The significantly positive correlation between black carbon (BC) and CCN at 1% supersaturation indicates that a percentage of the BC measured at the site may be in the form of an internal mixture and participated in the formation of CCN.

Yu, Shao-Cai↗

Nighttime Cirrus Detection using Atmospheric Infrared Sounder Window Channels and Total Column Water Vapor

A method of cirrus detection at nighttime is presented that utilizes 3.8 and 10.4 (micro)m infrared (IR) window brightness temperature differences (dBT) and total column precipitable water (PW) measurements. This technique is applied to the Atmospheric Infrared Sounder (AIRS) and Advanced Microwave Sounding Unit A (AMSU-A) instrument suite on board EOS-Aqua, where dBT is determined from sets of carefully selected AIRS window channels, while PW is derived from the synergistic AIRS and AMSU-A water vapor retrievals. Simulated and observed dBT for a particular value of PW are not constant; several physical factors impact dBT, including the variability in temperature and relative humidity profiles, surface emissivity, instrument noise, and skin/ near-surface air temperature differences. We simulate clear-sky dBT over a realistic range of PWs using 8350 radiosondes that have varying temperature and relative humidity profiles. Thresholds between cloudy and uncertain sky conditions are derived once the scatter in the clear-sky dBT is determined. Simulations of optically thin cirrus indicate that this technique is most sensitive to cirrus optical depth in the 10 (micro)m window of 0.1-0.15 or greater over the tropical and subtropical oceans, where surface emissivity and skin/near-surface air temperature impacts on the IR radiances are minimal. The method at present is generally valid over oceanic regions only, specifically, the tropics and subtropics. The detection of thin cirrus, and other cloud types, is validated using observations at the Atmospheric Radiation Measurement (ARM) program site located at Manus Island in the tropical western Pacific for 89 coincident EOS-Aqua overpasses. Even though the emphasis of this work is on the detection of thin cirrus at nighttime, this technique is sensitive to a broad cloud morphology. The cloud detection technique agrees with ARM-detected clouds 82-84% of the time, which include thin cirrus, as well as other cloud types. Most of the disagreements are well explained by AIRS footprint-scale heterogeneity compared to ARM point measurements, cirrus overlying lower-layer water clouds, possible mixed phase microphysics in midlevel clouds, and significant IR channel noise for cold BT scenes over deep convective towers.

Atmospheric Radiation Measurement (RAM)↗

U.S. IMERG Status

The U.S. Science Team’s Integrated Multi-satellitE Retrievals for the Global Precipitation Measurement (GPM) mission (IMERG) product provides estimates of surface precipitation rate and related information on a global 0.1° half-hour grid. It is run three times at increasingly longer latency and higher information input to serve different communities. This presentation will briefly summarize the major upgrades included in Version 07. The Goddard Profiling (GPROF) algorithm (applied to passive microwave sensor data from the GPM virtual constellation) and the Combined Radar-Radiometer Algorithm (CORRA) that provide input to IMERG V07 are both improved, and the new Precipitation Estimation from Remotely Sensed Information Using Artificial Neural Networks–Dynamic Infrared Rain Rate (PDIR) algorithm is being applied to infrared data, which employs an additional, warmer infrared temperature threshold than the previous infrared scheme and a deep neural network. V07 has improved bias performance as a result of calibrations that now employ the entire swath widths of CORRA and GPROF GPM Microwave Imager precipitation estimates. As well, time continuity in precipitation features is improved as a result of changes to the Kalman filter that approximately preserve the local histogram of precipitation rates (Scheme for Histogram Adjustment with Ranked Precipitation Estimates in the Neighborhood, or SHARPEN), and that better account for differences in sensor performance. A long-standing bug in the geolocation that shifted grid values 0.1° to the east in the latitude band 70°N-S has been corrected. Other changes in V07 include a hierarchical selection among motion vector sources to address deficiencies in the precipitation propagation near orography, an update to the precipitation phase specification for improved consistency with current inputs, and a renewed effort to implement climatological gauge adjustment to the near-real-time Runs. Early evaluations of V07 IMERG show interesting behavior across the TRMM orbit boost that is highly relevant to the planned orbit boost for the GPM Core observatory.

GPM↗

Identifying Chemical Aerosol Signatures Using Optical Suborbital Observations: How Much Can Optical Properties Tell us about Aerosol Composition?

Improvements in air quality and Earth’s climate predictions require improvements of the aerosol speciation in chemical transport models, using observational constraints. Aerosol speciation (e.g., organic aerosols, black carbon, sulfate, nitrate, ammonium, dust or sea salt) is typically determined using in situ instrumentation. Continuous, routine surface network aerosol composition measurements are not uniformly widespread over the globe. Satellites, on the other hand, can provide a maximum coverage of the horizontal and vertical atmosphere but observe aerosol optical properties (and not aerosol speciation) based on remote sensing instrumentation. Combinations of satellite-derived aerosol optical properties can inform on air mass aerosol types (AMTs e.g., clean marine, dust, polluted continental). However, these AMTs are subjectively defined, might often be misclassified and are hard to relate to the critical parameters that need to be refined in models. In this paper, we derive AMTs that are more directly related to sources and hence to speciation. They are defined, characterized, and derived using simultaneous in situ gas-phase, chemical and optical instruments on the same aircraft during the Study of Emissions and Atmospheric Composition, Clouds, and Climate Coupling by Regional Surveys (SEAC4RS, US, summer of 2013). First, we prescribe well-informed AMTs that display distinct aerosol chemical and optical signatures to act as a training AMT dataset. These in situ observations reduce the errors and ambiguities in the selection of the AMT training dataset. We also investigate the relative skill of various combinations of aerosol optical properties to define AMTs and how much these optical properties can capture dominant aerosol speciation. We find distinct optical signatures for biomass burning (from agricultural or wildfires), biogenic and dust-influence AMTs. Useful aerosol optical properties to characterize these signatures are the extinction angstrom exponent (EAE), the single scattering albedo, the difference of single scattering albedo in two wavelengths, the absorption coefficient, the absorption angstrom exponent (AAE), and the real part of the refractive index (RRI). We find that all four AMTs studied when prescribed using mostly airborne in situ gas measurements, can be successfully extracted from at least three combinations of airborne in situ aerosol optical properties (e.g., EAE, AAE and RRI) over the US during SEAC4RS. However, we find that the optically based classifications for BB from agricultural fires and polluted dust include a large percentage of misclassifications that limit the usefulness of results relating to those classes. The technique and results presented in this study are suitable to develop a representative, robust and diverse source-based AMT database. This database could then be used for widespread retrievals of AMTs using existing and future remote sensing suborbital instruments/networks. Ultimately, it has the potential to provide a much broader observational aerosol data set to evaluate chemical transport and air quality models than is currently available by direct in situ measurements. This study illustrates how essential it is to explore existing airborne datasets to bridge chemical and optical signatures of different AMTs, before the implementation of future spaceborne missions (e.g., the next generation of Earth Observing System (EOS) satellites addressing Aerosol, Cloud, Convection and Precipitation (ACCP) designated observables).

Meloe S F Kacenelenbogen↗

Canadian Space Agency Space Station Freedom utilization plans

Under the terms of the NASA/CSA Memorandum of Understanding, Canada will contribute the Mobile Servicing System and be entitled to use 3 percent of all Space Station utilization resources and user accommodations over the 30 year life of the Station. Equally importantly Canada, like NASA, can begin to exploit these benefits as soon as the Man-Tended Capability (MTC) phase begins, in early 1997. Canada has been preparing its scientific community to fully utilize the Space Station for the past five years; most specifically by encouraging, and providing funding, in the area of Materials Science and Applications, and in the area of Space Life Sciences. The goal has been to develop potential applications and an experienced and proficient Canadian community able to effectively utilize microgravity environment facilities such as Space Station Freedom. In addition, CSA is currently supporting four facilities; a Laser Test System, a Large Motion Isolation Mount, a Canadian Float Zone Furnace, and a Canadian Protein Crystallization Apparatus. In late April of this year CSA sent out a Solicitation of Interest (SOI) to potential Canadian user from universities, industry, and government. The intent of the SOI was to determine who was interested, and the type of payloads which the community at large intended to propose. The SOI will be followed by the release of an Announcement of Opportunity (AO) following governmental approval of the Long Term Space plan later this year, or early next year. Responses to the AO will be evaluated and prioritized in a fair and impartial payload selection process, within the guidelines set by our international partners and the Canadian Government. Payload selection is relatively simple compared to the development and qualification process. An end-to-end user support program is therefore also being defined. Much of this support will be provided at the new headquarters currently being built in St. Hubert, Quebec. It is recognized that utilizing the Space Station could be expensive for users; costing in many cases millions of dollars to get a payload from conception to retrieval. It is also recognized that some of the potential users cannot or will not invest a lot of money or effort into Space Station utilization, unless there is a perceived significant commercial potential. How best to fund Space Station payloads is under study. Space Station Freedom will provide the first opportunity for Canada to conduct experiments in a long-duration microgravity environment. CSA have been developing and funding potential users for some time, and considerable interest has been shown by the response to our SOI earlier this year. Canada can be one of the two earliest users for the Space Station, along with NASA. We hope to take full advantage of this opportunity.

Faulkner, James↗