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At least 19 records

Effect of PdO on TiO(sub2) Loading on Chemochromic Detection of Hydrogen

Safety is always a concern in all applications that utilize hydrogen (H(sub2)) in one form or the other. Hydrogen leaks are invisible and odorless. In addition, blending odorants or additives into hydrogen in a manner similar to natural gas is generally undesirable for certain applications including proton exchange membrane fuel cells. To facilitate detection of the location of hydrogen leaks, a special chemochromic H(sub2) sensing material that employs titania (Ti0(sub2)) supported palladium oxide (PdO) pigments encapsulated within a special silicone matrix has been developed at the Florida Solar Energy Center (FSEC). Several batches of PdO H(sub2) sensing pigments were synthesized using various Ti0(sub2) supports and their hydrogen detection activity determined. TEM and Particle size distribution analysis showed that smaller particles with hemispherical crystalline structure produced faster coloration kinetics when exposed to H(sub2) gas. However, uniformly distributed PdO particles on the Ti0(sub2) surface displayed greater color contrast, quantified by delta epsilon measurements. XRD analysis indicated that the crystalline phase of Ti0(sub2) had no effect on the chemochromic performance of the pigments in laboratory environment.

Mohajeri, Nahid↗

Transition metal oxides - CrO, MoO, NiO, PdO, AgO

The transition-metal oxides are quite ionic; Mulliken population analyses for several oxides give a negative charge of about 0.7 electrons for oxygen. When the transition-metal d shell is only partially filled, the orbitals are involved in covalent bonds with O; both two-electron bonding (2)-antibonding (0) and one-electron bonding (2)-antibonding (1) bonds are formed. These covalent bonds occur in addition to the ionic bonding. There is d-sigma-O2 p sigma repulsion, and this repulsion is reduced when the d-sigma electron is promoted into an orbital which has dominantly 4sp-sigma character and is polarized away from O.

Bauschlicher, C. W., Jr.↗

North Pacific Decadal Variability in the GEOS-5 Atmosphere-Ocean Model

This study examines the mechanisms of the Pacific decadal oscillation (PDO) in the GEOS-5 general circulation model. The model simulates a realistic PDO pattern that is resolved as the first empirical orthogonal function (EOF) of winter sea surface temperature (SST). The simulated PDO is primarily forced by Aleutian low through Ekman transport and surface fluxes, and shows a red spectrum without any preferred periodicity. This differs from the observations, which indicate a greater role of El Nino-Southern Oscillation (ENSO) forcing, and likely reflects the too short time scale of the simulated ENSO. The geostrophic transport in response to the Aleutian low is limited to the Kuroshio-Oyashio Extension, and is unlikely the main controlling factor in this model, although it reinforces the Ekman-induced SST anomalies. The delay between the Aleutian low and the PDO is relatively short (1 year) suggesting that the fast Ekman response (rather than Rossby wave propagation) sets the SST pattern immediately following an Aleutian low fluctuation. The atmospheric feedback (response to the SST) is only about 25 of the forcing and never evolves into an Aleutian low completely, instead projecting onto the North Pacific Oscillation (NPO), a meridional dipole in sea level pressure (SLP). The lack of preferred periodicity and weak atmospheric response bothindicate a coupled oscillation is an unlikely mechanism for the PDO in this model. In agreement with recent studies, the NPO is correlated with the North Pacific Gyre Oscillation (NPGO), which is another leading EOF of the North Pacific SST. A possible connection between the PDO and the NPGO is discussed.

Pacific Decadal Variability↗

Influences of the El Nino Southern Oscillation and the Pacific Decadal Oscillation on the Timing of the North American Spring

Detrended, modelled first leaf dates for 856 sites across North America for the period 1900-2008 are used to examine how the El Nino Southern Oscillation (ENSO) and the Pacific Decadal Oscillation (PDO) separately and together might influence the timing of spring. Although spring (mean March through April) ENSO and PDO signals are apparent in first leaf dates, the signals are not statistically significant (at a 95% confidence level (p <0.05)) for most sites. The most significant ENSO/PDO signal in first leaf dates occurs for El Nino and positive PDO conditions. An analysis of the spatial distributions of first leaf dates for separate and combined ENSO/PDO conditions features a northwest-southeast dipole that is significantly (at p <0.05) different than the distributions for neutral conditions. The nature of the teleconnection between Pacific SST's and first leaf dates is evident in comparable composites for detrended sea level pressure (SLP) in the spring months. During positive ENSO/PDO, there is an anomalous flow of warm air from the southwestern US into the northwestern US and an anomalous northeasterly flow of cold air from polar regions into the eastern and southeastern US. These flow patterns are reversed during negative ENSO/PDO. Although the magnitudes of first leaf date departures are not necessarily significantly related to ENSO and PDO, the spatial patterns of departures are significantly related to ENSO and PDO. These significant relations and the long-lived persistence of SSTs provide a potential tool for forecasting the tendencies for first leaf dates to be early or late.

McCabe, Gregory J.↗

North Pacific Decadal Variability: Insights from a Biennial ENSO Environment

This study examines the mechanisms of the Pacific decadal oscillation (PDO) in the NASA GEOS-5 general circulation model (GCM). Similar to several other state-of-the-art GCMs, the El Niño-Southern Oscillation (ENSO) simulated by the GEOS-5 has a strong biennial periodicity. Since this is a model bias that precludes a strong role of ENSO, it provides a unique environment to assess the other leading mechanisms of North Pacific decadal variability. Despite the biennial ENSO periodicity, the model simulates a realistic PDO pattern in the North Pacific that is resolved as the first empirical orthogonal function (EOF) of winter mean sea surface temperature (SST). The spectrum of the PDO indicates no preferred periodicity. The SST anomalies associated with the PDO, particularly its basin wide structure, are primarily forced by the Aleutian low through Ekman transport. The slow geostrophic transport in association with the meridional adjustment of the subtropical gyre is limited to a narrow region in the Kuroshio-Oyashio extension, north of 40degN. The atmosphere's response to the PDO, while weak, projects onto the North Pacific Oscillation (NPO), a meridional dipole in sea level pressure. Both the lack of preferred periodicity and the weak atmospheric response indicate an air-sea coupled oscillation is an unlikely mechanism in this model. In agreement with recent studies, the NPO is correlated with the North Pacific Gyre Oscillation, which is another leading EOF of North Pacific SST variability. The results emphasize the role of atmospheric variability in the North Pacific SST modes, thereby bringing into question the potential for their predictability.

GCM↗

Long-Term Changes/Trends in Surface Temperature and Precipitation During the Satellite Era (1979-2012)

During the post-1979 period in which the satellite-based precipitation measurements with global coverage are available, global mean surface temperature rapidly increased up to late 1990s, followed by a period of temperature hiatus after about 19981999. Comparing observed surface temperature trends against the simulated ones by the CMIP5 historical experiments especially in the zonal mean context suggests that although the anthropogenic greenhouse-gases (GHG) forcing has played a major role, in addition to the anthropogenic aerosols and various natural forcings, the effects from decadal-to-interdecadal scale internal modes specifically the Pacific Decadal Oscillation(PDO) are also very strong. Evident temperature changes associated with the PDOs phase shift are seen in the Pacific basin, with decadal-scale cooling in the tropical central-eastern Pacific and most of the east basin and concurrent warming in the subtropics of both hemispheres,even though the PDOs net effect on global mean temperature is relatively weak. The Atlantic Multidecadal Oscillation(AMO) also changed its phase in the mid-1990s, and hence its possible impact is estimated and assessed as well.However, comparisons with CMIP5 simulations suggest that the AMO may have not contributed as significantly as the PDO in terms of the changes trends in global surface temperature, even though the data analysis technique used here suggests otherwise. Long-term precipitation changes or trends during the post-1979 period are further shown to have been modulated by the two major factors:anthropogenic GHG and PDO, in addition to the relatively weak effects from aerosols and natural forcings. The spatial patterns of observed precipitation trends in the Pacific,including reductions in the tropical central-eastern Pacific and increases in the tropical western Pacific and along the South Pacific Convergence Zone, manifest the PDOs contributions.Removing the PDO effect from the total precipitation trends makes the spatial structures of precipitation trends more similar to those simulated by CMIP5 historical full forcing experiments particularly in the context of zonal-mean results. This also confirms that in spite of the PDO effect specifically on regional scales, the anthropogenic GHG signals are still discernible in observed precipitation during the time period. Following the increase of GHG, precipitation tends to increase roughly along the climatological ITCZ and decrease south of the equator and in the subtropics of both hemispheres.

GPCP↗

The Response of African Land Surface Phenology to Large Scale Climate Oscillations

Variations in agricultural production due to rainfall and temperature fluctuations are a primary cause of food insecurity on the African continent. Analysis of changes in phenology can provide quantitative information on the effect of climate variability on growing seasons in agricultural regions. Using a robust statistical methodology, we describe the relationship between phenology metrics derived from the 26 year AVHRR NDVI record and the North Atlantic Oscillation index (NAO), the Indian Ocean Dipole (IOD), the Pacific Decadal Oscillation (PDO), and the Multivariate ENSO Index (MEI). We map the most significant positive and negative correlation for the four climate indices in Eastern, Western and Southern Africa between two phenological metrics and the climate indices. Our objective is to provide evidence of whether climate variability captured in the four indices has had a significant impact on the vegetative productivity of Africa during the past quarter century. We found that the start of season and cumulative NDVI were significantly affected by large scale variations in climate. The particular climate index and the timing showing highest correlation depended heavily on the region examined. In Western Africa the cumulative NDVI correlates with PDO in September-November. In Eastern Africa the start of the June-October season strongly correlates with PDO in March-May, while the PDO in December-February correlates with the start of the February-June season. The cumulative NDVI over this last season relates to the MEI of March-May. For Southern Africa, high correlations exist between SOS and NAO of September-November, and cumulative NDVI and MEI of March-May. The research shows that climate indices can be used to anticipate late start and variable vigor in the growing season of sensitive agricultural regions in Africa.

Brown, Molly E.↗

The semiconductivity and stability of palladium oxide

Palladium metal films are prepared on quartz substrates by RF sputtering from a pure palladium target in an argon atmosphere. These films are then oxidized in air or in an oxygen atmosphere at 700 C for periods between 24 hr and 6 days. Either treatment is found to produce good-quality thin films of PdO with a uniform orange transmission. Attention is focused on optical and electrical conductivity measurements made on PdO films with a view toward determining their band gap, conductivity and thermal stability in vacuum and in the presence of oxygen. It is shown that hydrogen greatly reduces the thermal stability of PdO. The film decomposes to Pd metal by 350 K in the presence of hydrogen as compared to a temperature of about 580 K in vacuum.

Rey, E.↗

Understanding Changes in Water Availability in the Rio Grande/Rio Bravo del Norte Basin Under the Influence of Large-Scale Circulation Indices Using the Noah Land Surface Model

Water availability plays an important role in the socio-economic development of a region. It is however, subject to the influence of large-scale circulation indices, resulting in periodic excesses and deficits. An assessment of the degree of correlation between climate indices and water availability, and the quantification of changes with respect to major climate events is important for long-term water resources planning and management, especially in transboundary basins as it can help in conflict avoidance. In this study we first establish the correlation of the Pacific Decadal Oscillation (PDO) and El Nino-Southern Oscillation (ENSO) with gauged precipitation in the Rio Grande basin, and quantify the changes in water availability using runoff generated from the Noah land surface model. Both spatial and temporal variations are noted, with winter and spring being most influenced by conditions in the Pacific Ocean. Negative correlation is observed at the headwaters and positive correlation across the rest of the basin. The influence of individual ENSO events, classified using four different criteria, is also examined. El Ninos (La Ninas) generally cause an increase (decrease) in runoff, but the pattern is not consistent; percentage change in water availability varies across events. Further, positive PDO enhances the effect of El Nino and dampens that of La Nina, but during neutral/transitioning PDO, La Nina dominates meteorological conditions. Long El Ninos have more influence on water availability than short duration high intensity events. We also note that the percentage increase during El Ninos significantly offsets the drought-causing effect of La Ninas.

Khedun, C. Prakash↗

Covariability of Climate and Streamflow in the Upper Rio Grande from Interannual to Interdecadal Timescales

Study region: The Upper Rio Grande (URG) flows from its headwaters in Colorado, U.S., and provides an important source of water to millions of people in the U.S. states of Colorado, New Mexico, Texas, and also Mexico. Study focus: We reassess the explanatory power of the relationship of sea surface temperatures (SST) on URG streamflow variability on interannual to interdecadal timescales. We find a significant amount of the variance of spring-summer URG streamflow cannot be fully explained by SST. New hydrological insights: We find that the interdecadal teleconnection between SST and streamflow is more clear than on interannual timescales. The highest ranked years tend to be clustered during positive phases of the Pacific Decadal Oscillation (PDO). During the periods of decadal high flow (1900-1920, and 1979-1995), Pacific SST resembles a positive PDO pattern and the Atlantic a negative Atlantic Multidecadal Oscillation (AMO) pattern; an interbasin pattern shown in prior studies to be conducive to high precipitation and streamflow. To account for the part of streamflow variance not explained by SST, we analyze atmospheric Reanalysis data for the months preceding the highest spring-summer streamflow events. A variety of atmospheric configurations are found to precede the highest flow years through anomalous moisture convergence. This lack of consistency suggests that, on interannual timescales, weather and not climate can dominate the generation of high streamflow events.

AMO↗

X-Ray Photoelectron Spectroscopy Study of the Heating Effects on Pd/6H-SiC Schottky Structure

X-ray photoelectron spectroscopy is used to study the effects of heat treatment on the Pd/6H-SiC Schottky diode structure. After heating the structure at 425 C for 140 h, a very thin surface layer of PdO mixed with SiO(x) formed on the palladium surface of the Schottky structure. Heat treatment promoted interfacial diffusion and reaction which significantly broadened the interfacial region. In the interfacial region, the palladium concentration decreases with depth, and the interfacial products are Pd(x)Si (x = 1,2,3,4). In the high Pd concentration regions, Pd4Si is the major silicide component while gr and Pd2Si are major components in the low Pd concentration region. At the center of the interface, where the total palladium concentration equals that of silicon, the concentrations of palladium associated with various palladium silicides (Pd(x)Si, x= 1,2,3,4) are approximately equal. The surface passivation layer composed of PdO and SiO, may significantly affect the electronic and catalytic properties of the surface of the Schottky diode which plays a major role in gas detection. The electronic properties of the Schottky structure may be dominated by a (Pd+Pd(x)Si)/SiC interface. In order to stabilize the properties of the Schottky structure the surface and interface diffusion and reactions must be controlled.

Chen, Liang-Yu↗

Time-Variable Gravity Signal Due to Extratropic Pacific Water Mass Redistribution

Cox and Chao [2002] reported the detection of a large anomaly in the form of a positive "jump" in the time series of Earth's lowest-degree gravity harmonic J2, or the dynamic oblateness, during 1998. This prompted us to examine the mass redistribution in the global oceans. We report here a seesaw of the sea-surface height (SSH) in the extratropic north + south Pacific basins -- the leading (nonseasonal) EOF/PC mode in SSH derived from the 10-year TOPEX/Poseidon altimetry data in the extratropic Pacific region. The mode underwent a step-like jump with time evolution that match remarkably well with the observed J2 anomaly. However, the magnitude is several times too small to explain the observed J2, even if assuming the SSH jump was all mass-induced (as opposed to any steric effect which causes no time-variable gravity signal). If one accepts the notion that this extratropic Pacific seesaw is part of the geophysical process that produced the observed 1998 J2 anomaly, then this finding suggests strong geophysical connection of the interannual-to-decadal variation of J2 with the Pacific Decadal Oscillation (PDO), as the time series of the above EOF/PC mode is actually a formally defined PDO Index series.

Chao, Benjamin F.↗

Time-Variable Gravity Signal due to Extratropic Pacific Water Mass Redistribution

Using the satellite-laser-ranging (SLR) data, Cox and Chao [2002] reported the detection of a large post-1998 anomaly (in the form of a positive jump) in the time series of Earth s lowest-degree gravity harmonic 52, or the dynamic oblateness. Among several groups now examining the mass redistribution in the global geophysical fluids in search of the cause(s), we report here a temporally coinciding anomalies found in the extratropic north + south Pacific basins. Clearly seen in the leading EOFPC mode for extratropic Pacific, these anomalies occurred in sea-surface height, sea-surface temperature, and temperature- and salinity-depth profiles. We based our analysis on two different data sources: TOPEX/Poseidon altimetry, and the ECCO ocean general circulation model output assimilating T/P data. The magnitude of these changes, when converted to equivalent J2 change, appears to be a few times too small to explain the observed J2 directly. These findings, and the fact that the anomalies occurred following the strong 1997-98 El Nino, suggest strong geophysical connection of the interannual-to-decadal variation of 52 with the Pacific Decadal Oscillation (PDO) and the ultimate global-change processes that cause PDO. More work is underway, and additional independent data sources are examined, paying close attention to the fact that the J2 anomaly has been reversing back to normal since 2001. These include: (1) cryospheric contributions (melting of glaciers and ice sheets); (2) land hydrological contributions; (3) polar sea influences ( e g , via deep flow); (4) fluid flow in Earth's core; (5) time-variable gravity signals from SLR in higher harmonic degree/order, including J3,J4, (2,1), and (2,2) coefficients, considering their lower signal-to-noise ratios; (6) Earth rotation data in terms of length-of-day and polar motion.

Chao, B. F.↗

Representation of Modes of Variability in 6 U.S. Climate Models

We compare the performance of several modes of variability across six US climate modeling groups, with a focus on identifying robust improvements in recent models (including those participating in the Coupled Model Intercomparison Project (CMIP) Phase 6) compared to previous versions. In particular, we examine the representation of the Madden-Julian Oscillation (MJO), the El Ni˜no/Southern Oscillation (ENSO), the Pacific Decadal Oscillation (PDO), the Quasi-Biennial Oscillation (QBO) in the tropical stratosphere and the dominant modes of extra-tropical variability, including the Southern Annular Mode (SAM), the Northern Annular Mode (NAM) (and the closely related North Atlantic Oscillation (NAO)), and the Pacific-North American Pattern (PNA). Where feasible, we explore the processes driving these improvements through the use of “intermediary” experiments that utilize model versions between CMIP3/5 and CMIP6 as well as targeted sensitivity experiments in which individual modeling parameters are altered. We find clear and systematic improvements in the MJO and QBO and in the teleconnection patterns associated with the PDO and ENSO. Some gains arise from better process representation, while others (e.g. the QBO) from higher resolution that allows for a greater range of interactions. Our results demonstrate that the incremental development processes in multiple climate model groups lead to more realistic simulations over time.

Modes of variability↗

Hydrogen production by photoelectrolytic decomposition of H2O using solar energy

Photoelectrochemical systems for the efficient decomposition of water are discussed. Semiconducting d band oxides which would yield the combination of stability, low electron affinity, and moderate band gap essential for an efficient photoanode are sought. The materials PdO and Fe-xRhxO3 appear most likely. Oxygen evolution yields may also be improved by mediation of high energy oxidizing agents, such as CO3(-). Examination of several p type semiconductors as photocathodes revealed remarkable stability for p-GaAs, and also indicated p-CdTe as a stable H2 photoelectrode. Several potentially economical schemes for photoelectrochemical decomposition of water were examined, including photoelectrochemical diodes and two stage, four photon processes.

Rauh, R. D.↗

Miniaturized Metal (Metal Alloy)/PdO(x)/SiC Hydrogen and Hydrocarbon Gas Sensors

A miniaturized Schottky diode hydrogen and hydrocarbon sensor and the method of making same is disclosed and claimed. The sensor comprises a catalytic metal layer, such as palladium, a silicon carbide substrate layer and a thin barrier layer in between the catalytic and substrate layers made of palladium oxide (PdO(x)). This highly stable device provides sensitive gas detection at temperatures ranging from at least 450 to 600 C. The barrier layer prevents reactions between the catalytic metal layer and the substrate layer. Conventional semiconductor fabrication techniques are used to fabricate the small-sided sensors. The use of a thicker palladium oxide barrier layer for other semiconductor structures such as a capacitor and transistor structures is also disclosed.

Hunter, Gary W.↗

The US CLIVAR Working Group on Drought: A Multi-Model Assessment of the Impact of SST Anomalies on Regional Drought

The US CLIVAR working group on drought recently initiated a series of global climate model simulations forced with idealized SST anomaly patterns, designed to address a number of uncertainties regarding the impact of SST forcing and the role of land-atmosphere feedbacks on regional drought. Specific questions that the runs are designed to address include: What are mechanisms that maintain drought across the seasonal cycle and from one year to the next. What is the role of the land? What is the role of the different ocean basins, including the impact of EL Nino/Southern Oscillation (ENSO), the Pacific Decadal Oscillation (PDO), the Atlantic Multi-decadal Oscillation (AMO), and warming trends in the global oceans? The runs were done with several global atmospheric models including NASA/NSIPP-1, NCEP/GFS, GFDL/AM2, and NCAR CCM3 and CAM3. In addition, runs were done with the NCEP CFS (coupled atmosphere-ocean) model by employing a novel adjustment technique to nudge the coupled model towards the imposed SST forcing patterns. This talk provides an overview of the experiments and some initial results.

Schubert, Siegfried↗