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At least 289 records · Page 16

On the Hiatus in the Acceleration of Tropical Upwelling Since the Beginning of the 21st Century

Chemistry-climate models predict an acceleration of the upwelling branch of the Brewer-Dobson circulation as a consequence of increasing global surface temperatures, resulting from elevated levels of atmospheric greenhouse gases. The observed decrease of ozone in the tropical lower stratosphere during the last decades of the 20th century is consistent with the anticipated acceleration of upwelling. However, more recent satellite observations of ozone reveal that this decrease has unexpectedly stopped in the first decade of the 21st century, challenging the implicit assumption of a continuous acceleration of tropical upwelling. In this study we use three decades of chemistry transport-model simulations (1980-2013) to investigate this phenomenon and resolve this apparent contradiction. Our model reproduces the observed tropical lower stratosphere ozone record, showing a significant decrease in the early period followed by a statistically robust trend-change after 2002. We demonstrate that this trend-change is correlated with corresponding changes in the vertical transport and conclude that a hiatus in the acceleration of tropical upwelling occurred during the last decade.

trends↗

Chemical templates of the Central Molecular Zone

Context . The Central Molecular Zone (CMZ) of the Milky Way exhibits extreme conditions, including high gas densities, elevated temperatures, enhanced cosmic-ray ionization rates, and large-scale dynamics. This makes it a perfect laboratory for astrochemical studies. With large-scale molecular surveys revealing increasing chemical and physical complexity in the CMZ, it is essential to develop robust methods to decode the chemical information embedded in this extreme region. Aims . A key step to interpreting the molecular richness found in the CMZ is building chemical templates tailored to its diverse conditions. In particular, understanding how CMZ environments affect shock and protostellar chemistry is crucial. The combined impact of high ionization, elevated temperatures, and dense gas remains insufficiently explored for observable tracers. Methods . For this study, we utilized UCLCHEM , a gas-grain time-dependent chemical model, to link physical conditions with their corresponding molecular signatures and identify key tracers of temperature, density, ionization, and shock activity. To achieve this, we ran a grid of models of shocks and protostellar objects representative of typical CMZ conditions, focusing on 24 species, including complex organic molecules. Results . Shocked and protostellar environments show distinct evolutionary timescales (≲10 4 vs. ≳10 4 years); 300 K emerges as a key temperature threshold for chemical differentiation. We find that cosmic-ray ionization and temperature are the main drivers of chemical trends. HCO + , H 2 CO, and CH 3 SH trace ionization, while HCO, HCO + , CH 3 SH, CH 3 NCO, and HCOOCH 3 show consistent abundance contrasts between shocks and protostellar regions over similar temperature ranges. Conclusions . We characterized the behavior of 24 species in protostellar and shock-related environments. While our models underpredict some complex organics in shocks, they reproduce observed trends for most species, supporting scenarios involving a need for recurring shocks in Galactic Center clouds and enhanced ionization toward Sgr B2(N2). Future work should assess the role of shock recurrence and metallicity in shaping chemistry.

Galaxy: center↗

ICESat-2 Pointing Calibration and Geolocation Performance

ICESat-2 science requirements are dependent on the accurate real-time pointing control (i.e., geolocation control) and postprocessed geolocation knowledge of the laser altimeter surface returns. Prelaunch pointing alignment errors and postlaunch pointing alignment variation result in large geolocation errors that must be calibrated on orbit. In addition, the changing sun-orbit geometry causes thermal-mechanical forced laser frame alignment variations at the orbit period and trends from days, weeks, and months. Early mission analysis computed precise postlaunch laser beam alignment calibration. The alignment calibration was uploaded to the spacecraft and enabled the pointing control performance to achieve 4.4 ± 6.0 m, a significant improvement over the 45 m (1 σ) mission requirement. Laser frame alignment calibrations are used to reduce the alignment bias and time variation, as well as the orbital variation contributions to geolocation knowledge error from 6 to 1.7 m (1 σ). Relative beam alignment of the six beams is calibrated and shown to contribute between 0.5 ± 0.1 m and 2.4 ± 0.2 m of remaining geolocation knowledge error. Independent geolocation assessment based on comparison to high-resolution digital elevation models agrees well with the calibration geolocation error estimates. The analysis demonstrates the ICESat-2 mission is performing far better than its geolocation knowledge requirement of 6.5 m (1 σ) after the laser frame alignment bias variation and orbital variation calibrations have been applied. Remaining geolocation error is beam dependent and ranges from 2.5 m for beam 6 to 4.4 m for beam 2 (mean + 1 σ).

S B Luthcke↗

Performance of a Model Rich Burn-quick Mix-lean Burn Combustor at Elevated Temperature and Pressure

As interest in pollutant emission from stationary and aero-engine gas turbines increases, combustor engineers must consider various configurations. One configuration of increasing interest is the staged, rich burn - quick mix - lean burn (RQL) combustor. This report summarizes an investigation conducted in a recently developed high pressure gas turbine combustor facility. The model RQL combustor was plenum fed and modular in design. The fuel used for this study is Jet-A which was injected from a simplex atomizer. Emission (CO2, CO, O2, UHC, NOx) measurements were obtained using a stationary exit plane water-cooled probe and a traversing water-cooled probe which sampled from the rich zone exit and the lean zone entrance. The RQL combustor was operated at inlet temperatures ranging from 367 to 700 K, pressures ranging from 200 to 1000 kPa, and combustor reference velocities ranging from 10 to 20 m/s. Variations were also made in the rich zone and lean zone equivalence ratios. Several significant trends were observed. NOx production increased with reaction temperature, lean zone equivalence ratio and residence time and decreased with increased rich zone equivalence ratio. NOx production in the model RQL combustor increased to the 0.4 power with increased pressure. This correlation, compared to those obtained for non-staged combustors (0.5 to 0.7), suggests a reduced dependence on NOx on pressure for staged combustors. Emissions profiles suggest that rich zone mixing is not uniform and that the rich zone contributes on the order of 16 percent to the total NOx produced.

Peterson, Christopher O.↗

Pulmonary diffusing capacity, capillary blood volume, and cardiac output during sustained microgravity

We measured pulmonary diffusing capacity (DL), diffusing capacity per unit lung volume, pulmonary capillary blood volume (Vc), membrane diffusing capacity (Dm), pulmonary capillary blood flow or cardiac output (Qc), and cardiac stroke volume (SV) in four subjects exposed to nine days of microgravity. DL in microgravity was elevated compared with preflight standing values and was higher than preflight supine because of the elevation of both Vc and Dm. The elevation in Vc was comparable to that measured supine in 1 G, but the increase in Dm was in sharp contrast to the supine value. We postulate that, in 0 G, pulmonary capillary blood is evenly distributed throughout the lung, providing for uniform capillary filling, leading to an increase in the surface area available for diffusion. By contrast, in the supine 1-G state, the capillaries are less evenly filled, and although a similar increase in blood volume is observed, the corresponding increase in surface area does not occur. DL and its subdivisions showed no adaptive changes from the first measurement 24 h after the start of 0 G to eight days later. Similarly, there were no trends in the postflight data, suggesting that the principal mechanism of these changes was gravitational. The increase in Dm suggests that subclinical pulmonary edema did not result from exposure to 0 G. Qc was modestly increased inflight and decreased postflight compared with preflight standing. Compared with preflight standing, SV was increased 46 percent inflight and decreased 14 percent in the 1st week postflight. There were temporal changes in Qc and SV during 0 G, with the highest values recorded at the first measurement, 24 h into the flight. The lowest values of Qc and SV occurred on the day of return.

Prisk, G. K.↗

ICESat-2 Pointing Calibration and Geolocation Performance

ICESat-2 science requirements are dependent on the accurate real-time pointing control (i.e. geolocation control) and post-processed geolocation knowledge of the laser altimeter surface returns. Pre-launch pointing alignment errors and post-launch pointing alignment variation result in large geolocation errors that must be calibrated on orbit. In addition, the changing sun-orbit geometry causes thermal-mechanical forced laser frame alignment variations at the orbit period and trends from days, weeks and months. Early mission analysis computed precise post-launch laser beam alignment calibration. The alignment calibration was uploaded to the spacecraft and enabled the pointing control performance to achieve 4.4 ± 6.0 m, a significant improvement over the 45 m (1 σ) mission requirement. Laser frame alignment calibrations are used to reduce the alignment bias and time variation, as well as the orbital variation contributions to geolocation knowledge error from 6 m to 1.7 m (1 σ). Relative beam alignment of the six beams is calibrated and shown to contribute between 0.5 ± 0.1 m and 2.4 ± 0.2 m of remaining geolocation knowledge error. Independent geolocation assessment based on comparison to high-resolution digital elevation models agrees well with the calibration geolocation error estimates. The analysis demonstrates the ICESat-2 mission is performing far better than its geolocation knowledge requirement of 6.5 m (1 σ) after the laser frame alignment bias variation and orbital variation calibrations have been applied. Remaining geolocation error is beam dependent and ranges from 2.5 m for beam 6 to 4.4 m for beam 2 (mean + 1 σ).

S. B. Luthcke↗

Effect of thermal aging on corrosion behavior of duplex stainless steels

Abstract Despite their exceptional mechanical and corrosion properties, duplex stainless steels (DSS) have not found widespread use in high-temperature applications due to concerns over thermal aging and embrittlement at elevated operational temperatures (> 300 °C). The present study investigated the effect of thermal aging time on the electrochemical properties of lean and standard grade DSS that are exposed to a range of pressurized water reactors containing LiOH and H 3 BO 3 . The results indicated that the electrolyte chemistry plays a significant role in the corrosion behavior of the DSS alloys. Corrosion resistance decreased with thermal aging time for all DSS alloys; however, standard grade DSS (2205 and 2209-w) alloys showed better corrosion resistance than lean grades (2003, 2101, 2101-w). The presence of dissolved oxygen in the electrolytes resulted in a significant increase in corrosion rate for the DSS alloys, but it did not affect the general trend of corrosion rates with aging time. All DSS alloys became vulnerable to pitting corrosion due to chloride addition, but the pitting resistance decreased with increasing thermal aging time. Increased boron B content resulted in degradation of corrosion resistance of the DSS alloys, while minor changes in pH did not show a significant change in corrosion resistance. Mechanical and metallurgical characterization coupled with electrochemical characterization of the DSS alloys gave a comprehensive insight into the effects of thermal aging on the electrochemical response of the DSS. Graphical abstract

Murkute, Pratik (ORCID:0000000278636346)↗

Metal–Oxo Cluster Formation Using Ammonium and Sulfate to Differentiate M IV (Th, U, Ce) Chemistries

Isolating isostructural compounds of tetravalent metals M IV (Zr, Hf, Ce, Th, U, Pu, Np) improves our understanding of metal hydrolysis and coordination behavior across the periodic table. These metals form polynuclear clusters typified by the hexamer [M IV 6 O 4 (OH) 4 ] 12+ . Exploiting the ammonium M IV -sulfate (Ce IV , Th IV , and U IV ) phase space targeting rapid crystallization, we isolate the common hexamer [M IV 6 (OH) 4 (O) 4 ] 12+ but with different numbers of capping sulfates and water molecules for Ce IV , Th IV , and U IV . Furthermore, these phases allowed a direct comparison of bonding trends across the series. Upon cocrystallization with the hexamers, higher complex structures can be identified. Thorium features assemblies with monomer-linked hexamer chains. Uranium features assemblies with sulfate-bridged hexamers and the supramolecular assembly of 14 hexamers into the U 84 , [U 6 (OH) 4 (O) 4 ) 14 (SO 4 ) 120 (H 2 O) 42 ] 72– . Last, cerium showcases the isolation from monomers to the Ce 62 , [Ce 62 (OH) 30 (O) 58 (SO 4 ) 71 (H 2 O) 33.25 ] 41– . Furthermore, small-angle X-ray scattering (room temperature) shows ammonium-induced cluster assembly for Ce IV but minimal reactivity for U IV and Th IV . In this study, because the phases crystallized at elevated temperature demonstrates favorable cluster assembly, these solution phase results were surprising and suggest some other characteristics such as Ce’s facile redox behavior, contributes to its solution-phase speciation.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Budding yeasts in the subphylum Saccharomycotina Genome sequencing and assembly

Eukaryotic life depends on the functional elements encoded by both the nuclear genome and organellar genomes, such as those contained within the mitochondria. The content, size, and structure of the mitochondrial genome varies across organisms with potentially large implications for phenotypic variance and resulting evolutionary trajectories. Among yeasts in the subphylum Saccharomycotina, extensive differences have been observed in various species relative to the model yeast Saccharomyces cerevisiae, but mitochondrial genome sampling across many groups has been scarce, even as hundreds of nuclear genomes have become available. By extracting mitochondrial reads from existing short-read genome sequence datasets, we have greatly expanded both the number of available genomes and the coverage across sparsely sampled clades. Comparison of 353 yeast mitochondrial genomes revealed that, while size and GC content were fairly consistent across species, those in the genera Metschnikowia and Saccharomyces trended larger, while several species in the order Saccharomycetales exhibited lower GC content. Extreme examples for both size and GC content were scattered throughout the subphylum. All mitochondrial genomes shared a core set of protein-coding genes for Complexes III, IV, and V, but they varied in the presence or absence of mitochondrially-encoded canonical Complex I genes. We traced the loss of Complex I genes to a major event in the ancestor of the orders Saccharomycetales and Saccharomycodales, but we also observed several independent losses in the orders Phaffomycetales, Pichiales, and Dipodascales. In contrast to prior hypotheses based on smaller-scale datasets, comparison of evolutionary rates in protein-coding genes showed no bias towards elevated rates among aerobically fermenting (Crabtree/Warburg-positive) yeasts. Mitochondrial introns were widely distributed, but highly enriched in some groups. The majority of mitochondrial introns were poorly conserved within groups, but several were shared within groups, between groups, and even across taxonomic orders, which is consistent with horizontal gene transfer, likely involving homing endonucleases acting as selfish elements. As the number of available fungal nuclear genomes continues to expand, the methods described here to retrieve mitochondrial genome sequences from these datasets will prove invaluable to ensuring that studies of fungal mitochondrial genomes keep pace with their nuclear counterparts.

diversity↗

Sequential versus Simultaneous Aging of XLPE Nuclear Cable Insulation Subjected to Elevated Temperature and Gamma Radiation

Electrical cables constitute a critical component of nuclear power generation. The aging behavior of electrical cable insulation under combined exposure to thermal and radiation stress is not additive, complicating lifetime prediction of cable performance based on sequential accelerated aging. In this work we explore the relative effects of simultaneous and sequential thermal and gamma radiation aging on cross-linked polyethylene (XLPE), which is commonly found in commercial nuclear power plants in the United States. Samples of XLPE were subjected to up to 320 kGy of gamma irradiation at a dose rate of 300 Gy/hr in two heating scenarios. In the first, simultaneously-aged samples were heated at 150°C during irradiation. In the second, sequentially aged samples were heated at 150°C for designated durations followed by corresponding periods of irradiation without heating. The mass, total color difference, and density were characterized to quantify aging of the insulation polymer. Sequential aging is hypothesized to be more damaging to XLPE insulation due to an increased trend in mass gain, total color difference, and density.

Cross-linked polyethylene, XLPE, nuclear cable, ac↗

Fire Station #2, Former Sewage Treatment Plant #17, and Towway Area-SWMU 114 PFAS Site Assessment Progress Report Kennedy Space Center, Florida

This PFAS Site Assessment Progress Report (SAPR) presents the findings of the 2022 PFAS investigation conducted from November 2021 through August 2022 at Solid Waste Management Unit (SWMU) 114 located within Kennedy Space Center (KSC), Florida. SWMU 114 includes area around Fire Station #2, Former Sewage Treatment Plant #17, the southern portion of the Shuttle Landing Facility Runway, Remote Launch Vehicle Hangar, and the Towway area. Fire Station #2 was constructed in 2008 and is currently active, housing fire station personnel and equipment, including aqueous film forming foam (AFFF). Releases of AFFF has occurred at SWMU 114. Previous environmental assessments have been performed at SWMU 114, including soil, groundwater, and surface water sampling for volatile organic compounds, polycyclic aromatic hydrocarbons, total petroleum hydrocarbons, and metals. No active remediation has been performed at the SWMU 114. PFAS site assessment field activities were conducted at SWMU 114 from November 2021 through August 2022. During the 2021-2022 Site Assessment, 124 direct-push samples were collected from 27 locations, 17 surface water samples were collected from 15 locations, 41 groundwater samples were collected from 37 newly installed monitoring wells, five concrete samples were collected from four locations, and one asphalt sample was collected. Additionally, two soil borings were advanced to 60 feet for lithologic descriptions, ten staff gauges were installed, and one round of water level measurements were collected from monitoring wells and staff gauges for groundwater flow determination. All groundwater and surface water samples were analyzed for 25 PFAS analytes by USEPA Method 537M. Concrete, and asphalt samples were analyzed by synthetic precipitation leaching procedure (SPLP) PFAS analysis by USEPA Modified Method 537M. Groundwater results were compared to the most recent Regional Screening Levels (RSLs) published by USEPA for residential tap water (USEPA, 2022a) to determine the extent of PFAS contamination at SWMU 114 for six PFAS analytes (PFOA, PFNA, PFBS, PFHxS, PFOS, and GenX). Surface water results were compared to the FDEP surface water screening levels (SW SLs) (FDEP, 2020) for PFOA and PFOS. The PFAS investigation concluded that groundwater exceeding RSLs extends east and south to Banana Creek and west to approximately the center of the SLF runway. The extent of PFAS is approximated to the north, to an area between Sharkey Road and Astronaut Road, where samples below the RSLs do not fully bound SWMU 114. At least two distinct PFAS source areas are located near Fire Station #2 and along Towway, at S114-MW0007S, within SWMU 114. Groundwater head measurements indicate that flow at SWMU 114 is generally similar across the shallow and intermediate water tables. A northeast to southwest trending groundwater divide is located near the middle of Towway where groundwater southeast of the divide flows to the south and groundwater northwest of the divide flows to the west. The groundwater divide generally separates the two areas of higher PFAS concentrations. Surface water samples indicated concentrations of PFOS above the SW SLs in surface water bodies across the site. Further assessment and sampling are required to better understand the interaction between groundwater and surface water at SWMU 114. Concrete and asphalt samples collected confirm that a significant release of AFFF occurred near the stormwater pond northwest of Fire Station #2. Additional concrete samples surrounding Fire Station #2 and at the northwest and southeast edges of the SLF tarmac indicate elevated PFOS concentrations. These results indicate that discharges of AFFF in these locations have infiltrated into asphalt and concrete and may act as a continuing source of PFAS to groundwater and surface water after rain events. Additional direct-push samples are required to delineate PFAS at SWMU 114. Samples may need to extend beyond the Former SLF Rescue Building and Morpheous Test Site to delineate PFAS in groundwater. Monitoring wells should be sampled and gauged quarterly to determine if seasonal impacts are observable, especially in shallow wells near surface water features. Furthermore, surface water samples should be collected from additional ditches to further define the extent of surface water impacts at SWMU 114 and extending along the SLF runway. Staff gauges should be gauged quarterly with groundwater gauging to determine surface water flow and interaction with groundwater. The PFAS sampling results and path forward for SWMU 114 were presented to the KSC Remediation Team in October 2022. Once the PFAS SAPR is approved, it will be submitted to the Florida Department of Environmental Protection.

Howard Franklin Fowler↗

Carbonate Platform Development and Stromatolite Morphogenesis: Constraints on Environmental and Biological Evolution

Work has been completed on the digital mapping of a terminal Proterozoic reef complex in Namibia. This complex formed an isolated carbonate platform developed downdip on a carbonate ramp of the Nama Group. The stratigraphic evolution of the platform was digitally reconstructed from an extensive dataset that was compiled by using digital surveying technologies. The platform comprises three accommodation cycles in which each subsequent cycle experienced progressively greater influence of a long-term accommodation increase. Aggradation and progradation during the first cycle resulted in a flat, uniform, sheet-like platform. The coarsening and shallowing-upward sequence representing the first cycle is dominated by columnar stromatolitic thrombolites and massive dolostones with interbedded mudstone-grainstone at the base of the sequence grading into cross-bedded dolostones. The second cycle features aggradation, formation of a distinct margin containing thrombolite mounds and domes, and the development of a bucket geometry. Columnar stromatolitic thrombolites dominate the platform interior. The final stage of platform development shows a deepening trend with initial aggradation and formation of well-bedded, thin deposits in the interior and mound development at the margins. While the interior drowned, the platform margin kept up with rising sea level and a complex pinnacle reef formed containing fused and coalesced thrombolite mounds flanked by bioclastic grainstones (containing Cloudina and Namacalathus fossils) and collapse breccias. A set of isolated large thrombolite mounds flanked by shales indicate the final stage of the carbonate platform. During a progressive increase in accommodation, a flat-topped isolated carbonate platform becomes aerially less extensive by either backstepping or formation of smaller pinnacles or a combination of both. The overall geometric evolution of the studied platform from flat-topped to bucket with elevated margins is recorded in many Proterozoic and Phanerozoic isolated carbonate platforms with similar dimensions. The terminal Proterozoic, microbial-dominated, isolated carbonate platform of this study clearly illustrates that the answer to accommodation changes was already familiar among carbonate platforms before the dawn of metazoan-dominated platforms.

Grotzinger, John P.↗

A Techno-Economic Analysis of a 50MWth Light-Trapping Cavity-Planar Solar Receiver Tower Capital Expenditures and its Cost Mitigation Strategies

To maximize thermal efficiency, the National Renewable Energy Laboratory (NREL) has proposed a light-trapping cavity-planar receiver design intended to capture energy from reradiating surfaces. This system implements a macroscale light trapping mechanism induced by panels with triangular channels, this mechanism allows for elevated temperatures on the receiver panels and in turn the temperature of the HTF; using this design coupled with the implementation of a fluidized particle flow as the HTF, it can be expected for some components to reach a peak working temperature of nearly 1000 degrees C cyclically throughout each day-night cycle. While these temperatures correlate to higher efficiency of the CSP tower they also demand intense thermomechanical properties from the materials used to make the receiver panels. In this analysis, we will list our assumptions to provide clarity on the significance of our calculation. This cost analysis will be conducted using a combination of both case study data and surveying industry to determine costs that are relevant to the current market trends. This analysis represents an early attempt to establish the Capital Expenditures required for a CSP tower of such design to determine the feasibility of implementing such a system in the industry.

concentrated solar power (CSP)↗

Geologic and mineral and water resources investigations in western Colorado, using Skylab EREP data

The author has identified the following significant results. Discovery of three major north-trending, throughgoing faults in the Front Range, previously mapped only as isolated segments, demonstrates the utility of space photography and may lead to reinterpretation of the Front Range tectonic style. Faulting and alteration appear to be the most useful indicators of mineralization in central Colorado. These phenomena appear on Skylab photography as tonal lineaments and color anomalies. Twenty-three lineaments have been mapped in the San Juan Mountains, the longest of which is 156 km long. Twelve lineaments intersect or are tangent to calderas. Intrusive domes are aligned along lineaments, but calderas appear to occur at the intersections of major lineaments. Lineaments can be recognized on some EREP passes but not on other passes over the same area. The difference is attributed to solar elevation effects. Bedding attitudes can be photogeologically estimated down to surprisingly low dips, on the order of + or - 1-2 deg, and attitudes can be subdivided easily into quantitative groups. The primary application of Skylab photography to geologic mapping in montane areas is clearly limited to regional mapping at scales smaller than 1:24,000.

Lee, K.↗

Applications of MODIS Fluorescent Line Height Measurements to Monitor Water Quality Trends and Algal Bloom Activity

Recent advances in satellite and airborne remote sensing, such as improvements in sensor and algorithm calibrations, processing techniques and atmospheric correction procedures have provided for increased coverage of remote-sensing, ocean-color products for coastal regions. In particular, for the Moderate Resolution Imaging Spectrometer (MODIS) sensor calibration updates, improved aerosol retrievals and new aerosol models has led to improved atmospheric correction algorithms for turbid waters and have improved the retrieval of ocean color in coastal waters. This has opened the way for studying ocean phenomena and processes at finer spatial scales, such as the interactions at the land-sea interface, trends in coastal water quality and algal blooms. Human population growth and changes in coastal management practices have brought about significant changes in the concentrations of organic and inorganic, particulate and dissolved substances entering the coastal ocean. There is increasing concern that these inputs have led to declines in water quality and have increase local concentrations of phytoplankton, which cause harmful algal blooms. In two case studies we present MODIS observations of fluorescence line height (FLH) to 1) assess trends in water quality for Tampa Bay, Florida and 2) illustrate seasonal and annual variability of algal bloom activity in Monterey Bay, California as well as document estuarine/riverine plume induced red tide events. In a comprehensive analysis of long term (2003-2011) in situ monitoring data and satellite imagery from Tampa Bay we assess the validity of the MODIS FLH product against chlorophyll-a and a suite of water quality parameters taken in a variety of conditions throughout a large optically complex estuarine system. A systematic analysis of sampling sites throughout the bay is undertaken to understand how the relationship between FLH and in situ chlorophyll-a responds to varying conditions and to develop a near decadal trend in water quality changes. In situ monitoring locations that correlated well with satellite imagery were in depths greater than seven meters and were located over five kilometers from shore. Water quality parameter of total nitrogen, phosphorous, turbidity and biological oxygen demand had high correlations with these sites, as well. Satellite FLH estimates show improving water quality from 2003-2007 with a slight decline up through 2011. Dinoflagellate blooms in Monterey Bay, California (USA) have recently increased in frequency and intensity. Nine years of MODIS FLH observations are used to describe the annual and seasonal variability of bloom activity within the Bay. Three classes of MODIS algorithms were correlated against in situ chlorophyll measurements. The FLH algorithm provided the most robust estimate of bloom activity. Elevated concentrations of phytoplankton were evident during the months of August-November, a period during which increased occurrences of dinoflagellate blooms have been observed in situ. Seasonal patterns of FLH show the on- and offshore movement of areas of high phytoplankton biomass between oceanographic seasons. Higher concentrations of phytoplankton are also evident in the vicinity of the land-based nutrient sources and outflows, and the cyclonic bay-wide circulation can transport these nutrients to the northern Bay bloom incubation region. Both of these case studies illustrate the utility MODIS FLH observations in supporting management decisions in coastal and estuarine waters.

Fischer, Andrew↗

Thermal barrier coating life prediction model development

This report describes work performed to determine the predominat modes of degradation of a plasma sprayed thermal barrier coating system and to develop and verify life prediction models accounting for these degradation modes. The primary TBC system consisted of a low pressure plasma sprayed NiCrAlY bond coat, an air plasma sprayed ZrO2-Y2O3 top coat, and a Rene' 80 substrate. The work was divided into 3 technical tasks. The primary failure mode to be addressed was loss of the zirconia layer through spalling. Experiments showed that oxidation of the bond coat is a significant contributor to coating failure. It was evident from the test results that the species of oxide scale initially formed on the bond coat plays a role in coating degradation and failure. It was also shown that elevated temperature creep of the bond coat plays a role in coating failure. An empirical model was developed for predicting the test life of specimens with selected coating, specimen, and test condition variations. In the second task, a coating life prediction model was developed based on the data from Task 1 experiments, results from thermomechanical experiments performed as part of Task 2, and finite element analyses of the TBC system during thermal cycles. The third and final task attempted to verify the validity of the model developed in Task 2. This was done by using the model to predict the test lives of several coating variations and specimen geometries, then comparing these predicted lives to experimentally determined test lives. It was found that the model correctly predicts trends, but that additional refinement is needed to accurately predict coating life.

Hillery, R. V.↗

Soil metabolome response to whole-ecosystem warming at the Spruce and Peatland Responses under Changing Environments experiment

In this study, a suite of complementary environmental geochemical analyses, including NMR and gas chromatography-mass spectrometry (GC-MS) analyses of central metabolites, Fourier transform ion cyclotron resonance mass spectrometry (FTICR-MS) of secondary metabolites, and lipidomics, was used to investigate the influence of organic matter (OM) quality on the heterotrophic microbial mechanisms controlling peatland CO2, CH4, and CO2:CH4 porewater production ratios in response to climate warming. Our investigations leverage the Spruce and Peatland Responses under Changing Environments (SPRUCE) experiment, where air and peat warming were combined in a whole-ecosystem warming treatment. We hypothesized that warming would enhance the production of plant-derived metabolites, resulting in increased labile OM inputs to the surface peat, thereby enhancing microbial activity and greenhouse gas production. Because shallow peat is most susceptible to enhanced warming, increases in labile OM inputs to the surface, in particular, are likely to result in significant changes to CO2 and CH4 dynamics and methanogenic pathways. In support of this hypothesis, significant correlations were observed between metabolites and temperature consistent with increased availability of labile substrates, which may stimulate more rapid turnover of microbial proteins. An increase in the abundance of methanogenic genes in response to the increase in the abundance of labile substrates was accompanied by a shift toward acetoclastic and methylotrophic methanogenesis. Our results suggest that as peatland vegetation trends toward increasing vascular plant cover with warming, we can expect a concomitant shift toward increasingly methanogenic conditions and amplified climate–peatland feedbacks.

Wilson, Rachel M.↗

CO 2 Hydrogenation on ZrO 2 /Cu(111) Surfaces: Production of Methane and Methanol

The conversion and utilization of carbon dioxide is a critical challenge for the control of greenhouse gas pollution and in the production of high value chemicals in C1 chemistry. ZrO 2 /Cu(111) is an inverse oxide/metal catalyst that displays high activity and stability for the hydrogenation of CO 2 into methanol at 500-600 K. At elevated temperatures, ZrO 2 grows on a CuO x /Cu(111) substrate forming islands of 10-12 nm in size and an average height of ~ 3 Å. Reaction with H 2 leads to the removal of the copper oxide producing ZrO 2 /Cu(111) surfaces which are very active for the binding and dissociation of CO 2 into CO and C. After exposing ZrO 2 /Cu(111) to moderate or elevated pressures of a CO 2 /H 2 mixture at 300 K, atomic C and minor amounts of CH x O and CO x are deposited on the catalyst surface. The adsorbed CH x O and CO x disappear upon heating above 400 K. The catalytic tests for CO 2 hydrogenation give CO as the main reaction product and CH 4 and CH 3 OH as secondary products. The relative yields of methane and methanol change with time and track the amount of atomic C deposited on the active ZrO 2 /Cu(111) surface. The formation of methane stops once the catalyst surface is saturated with C. Under steady-state conditions, ZrO 2 /Cu(111) is a much better catalyst for methanol synthesis than ZnO/Cu(111). This trend reflects variations in the size of the oxide islands and in the strength of oxide-metal interactions. The use of an inverse oxide/metal configuration is an important synthetic tool when preparing active, selective, and stable catalysts for CO 2 hydrogenation.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗