Showing papers by "Pacific Northwest National Laboratory published in 2004"

Advanced anodes for high-temperature fuel cells

Abstract: Fuel cells will undoubtedly find widespread use in this new millennium in the conversion of chemical to electrical energy, as they offer very high efficiencies and have unique scalability in electricity-generation applications. The solid-oxide fuel cell (SOFC) is one of the most exciting of these energy technologies; it is an all-ceramic device that operates at temperatures in the range 500–1,000 °C. The SOFC offers certain advantages over lower temperature fuel cells, notably its ability to use carbon monoxide as a fuel rather than being poisoned by it, and the availability of high-grade exhaust heat for combined heat and power, or combined cycle gas-turbine applications. Although cost is clearly the most important barrier to widespread SOFC implementation, perhaps the most important technical barriers currently being addressed relate to the electrodes, particularly the fuel electrode or anode. In terms of mitigating global warming, the ability of the SOFC to use commonly available fuels at high efficiency, promises an effective and early reduction in carbon dioxide emissions, and hence is one of the lead new technologies for improving the environment. Here, we discuss recent developments of SOFC fuel electrodes that will enable the better use of readily available fuels.

Glucose Biosensors Based on Carbon Nanotube Nanoelectrode Ensembles

Abstract: This paper describes the development of glucose biosensors based on carbon nanotube (CNT) nanoelectrode ensembles (NEEs) for the selective detection of glucose. Glucose oxidase was covalently immobilized on CNT NEEs via carbodiimide chemistry by forming amide linkages between their amine residues and carboxylic acid groups on the CNT tips. The catalytic reduction of hydrogen peroxide liberated from the enzymatic reaction of glucose oxidase upon the glucose and oxygen on CNT NEEs leads to the selective detection of glucose. The biosensor effectively performs a selective electrochemical analysis of glucose in the presence of common interferents (e.g., acetaminophen, uric and ascorbic acids), avoiding the generation of an overlapping signal from such interferers. Such an operation eliminates the need for permselective membrane barriers or artificial electron mediators, thus greatly simplifying the sensor design and fabrication.

Gas-Phase Databases for Quantitative Infrared Spectroscopy

Abstract: The National Institute of Standards and Technology (NIST) and the Pacific Northwest National Laboratory (PNNL) are each creating quantitative databases containing the vapor-phase infrared spectra of pure chemicals. The digital databases have been created with both laboratory and remote-sensing applications in mind. A spectral resolution of approximate, equals 0.1 cm(-1) was selected to avoid degrading sharp spectral features, while also realizing that atmospheric broadening typically limits line widths to 0.1 cm(-1). Calculated positional (wave- number, cm(-1)) uncertainty is /=9) path length-concentration burdens and fitting a weighted Beer's law plot to each wavenumber channel. The two databases include different classes of compounds and were compared using 12 samples. Though these 12 samples span a range of polarities, absorption strengths, and vapor pressures, the data agree to within experimental uncertainties with only one exception.

A common open representation of mass spectrometry data and its application to proteomics research

Abstract: A broad range of mass spectrometers are used in mass spectrometry (MS)-based proteomics research. Each type of instrument possesses a unique design, data system and performance specifications, resulting in strengths and weaknesses for different types of experiments. Unfortunately, the native binary data formats produced by each type of mass spectrometer also differ and are usually proprietary. The diverse, nontransparent nature of the data structure complicates the integration of new instruments into preexisting infrastructure, impedes the analysis, exchange, comparison and publication of results from different experiments and laboratories, and prevents the bioinformatics community from accessing data sets required for software development. Here, we introduce the 'mzXML' format, an open, generic XML (extensible markup language) representation of MS data. We have also developed an accompanying suite of supporting programs. We expect that this format will facilitate data management, interpretation and dissemination in proteomics research.

Identification of Proteins in Human Cytomegalovirus (HCMV) Particles: the HCMV Proteome

Abstract: Human cytomegalovirus (HCMV), a member of the herpesvirus family, is a large complex enveloped virus composed of both viral and cellular gene products. While the sequence of the HCMV genome has been known for over a decade, the full set of viral and cellular proteins that compose the HCMV virion are unknown. To approach this problem we have utilized gel-free two-dimensional capillary liquid chromatography-tandem mass spectrometry (MS/MS) and Fourier transform ion cyclotron resonance MS to identify and determine the relative abundances of viral and cellular proteins in purified HCMV AD169 virions and dense bodies. Analysis of the proteins from purified HCMV virion preparations has indicated that the particle contains significantly more viral proteins than previously known. In this study, we identified 71 HCMV-encoded proteins that included 12 proteins encoded by known viral open reading frames (ORFs) previously not associated with virions and 12 proteins from novel viral ORFs. Analysis of the relative abundance of HCMV proteins indicated that the predominant virion protein was the pp65 tegument protein and that gM rather than gB was the most abundant glycoprotein. We have also identified over 70 host cellular proteins in HCMV virions, which include cellular structural proteins, enzymes, and chaperones. In addition, analysis of HCMV dense bodies indicated that these viral particles are composed of 29 viral proteins with a reduced quantity of cellular proteins in comparison to HCMV virions. This study provides the first comprehensive quantitative analysis of the viral and cellular proteins that compose infectious particles of a large complex virus.

A bifunctional poly(ethylene glycol) silane immobilized on metallic oxide-based nanoparticles for conjugation with cell targeting agents.

Abstract: A trifluoroethylester-terminal poly(ethylene glycol) (PEG) silane was synthesized and self-assembled on iron oxide nanoparticles. The nanoparticle system thus prepared has the flexibility to conjugate with cell targeting agents via either carboxylic or amine terminal groups for a number of biomedical applications, including magnetic resonance imaging (MRI) and controlled drug delivery. The trifluoroethylester silane was synthesized by modifying a PEG diacid to form the corresponding bistrifluoroethylester (TFEE), followed by a reaction with 3-aminopropyltriethoxysilane (APS). The APS coupled with PEG chains confers the stability of PEG self-assembled monolayers (SAMs) and increases the PEG packing density on nanoparticles by establishing hydrogen bonding between the carbonyl and amine groups present within the monolayer structure. The success of the synthesis of the PEG TEFE silane was confirmed with (1)H NMR and Fourier transform infrared spectroscopy (FTIR). The conjugating flexibility of the PEG TEFE was demonstrated with folic acid that had carboxylic acid groups and amine terminal groups, respectively, and was confirmed by FTIR. TEM analysis showed the well-dispersed nanoparticles before and after they were coated with PEG and folic acid.

Regional climate modeling: Progress, challenges, and prospects

Abstract: Regional climate modeling with regional climate models (RCMs) has matured over the past decade and allows for meaningful utilization in a broad spectrum of applications. In this paper, latest progresses in regional climate modeling studies are reviewed, including RCM development, applications of RCMs to dynamical downscaling for climate change assessment, seasonal climate predictions and climate process studies, and the study of regional climate predictability. Challenges and potential directions of future research in this important area are discussed, with the focus on those to which less attention has been given previously, such as the importance of ensemble simulations, further development and improvement of regional climate modeling approach, modeling extreme climate events and sub-daily variation of clouds and precipitation, model evaluation and diagnostics, applications of RCMs to climate process studies and seasonal predictions, and development of regional earth system models. It is believed that with both the demonstrated credibility of RCMs’ capability in reproducing not only monthly to seasonal mean climate and interannual variability but also the extreme climate events when driven by good quality reanalysis and the continuous improvements in the skill of global general circulation models (GCMs) in simulating large-scale atmospheric circulation, regional climate modeling will remain an important dynamicalmore » downscaling tool for providing the needed information for assessing climate change impacts and seasonal climate predictions, and a powerful tool for improving our understanding of regional climate processes. An internationally coordinated effort can be developed with different focuses by different groups to advance regional climate modeling studies. It is also recognized that since the final quality of the results from nested RCMs depends in part on the realism of the large-scale forcing provided by GCMs, the reduction of errors and improvement in physics parameterizations in both GCMs and RCMs remain a priority for climate modeling community.« less

Thermosensitive Gold Nanoparticles

Abstract: Thermosensitive gold nanoparticles were fabricated by conjugating Au with a thiol-terminated poly(N-isopropylacrylamide) or PPA; this polymer stabilizer exhibits a temperature transition while undergoing a hydrophilic to hydrophobic transformation. The introduction of PPA onto gold nanoparticles has sensitized Au nanoparticles with unique temperature dependence. At low temperature (25 °C), the solutions containing PPA-functionalized gold nanoparticles are transparent, whereas higher temperatures (30 °C) lead to opaque suspensions. The thermosensitive property of PPA-functionalized Au nanoparticles is reversible, and the clear−opaque suspensions can be repeated many times.

Mid-Century Ensemble Regional Climate Change Scenarios for the Western United States

Abstract: To study the impacts of climate change on water resources in the western U.S., global climate simulations were produced using the National Center for Atmospheric Research/Department of Energy (NCAR/DOE) Parallel Climate Model (PCM). The Penn State/NCAR Mesoscale Model (MM5) was used to downscale the PCM control (20 years) and three future(2040–2060) climate simulations to yield ensemble regional climate simulations at 40 km spatial resolution for the western U.S. This paper describes the regional simulations and focuses on the hydroclimate conditions in the Columbia River Basin (CRB) and Sacramento-San Joaquin River (SSJ) Basin. Results based on global and regional simulations show that by mid-century, the average regional warming of 1 to 2.5 °C strongly affects snowpack in the western U.S. Along coastal mountains, reduction in annual snowpack was about70% as indicated by the regional simulations. Besides changes in mean temperature, precipitation, and snowpack, cold season extreme daily precipitation increased by 5 to 15 mm/day (15–20%) along theCascades and the Sierra. The warming resulted in increased rainfall at the expense of reduced snowfall, and reduced snow accumulation (or earlier snowmelt) during the cold season. In the CRB, these changes were accompanied by more frequent rain-on-snow events. Overall, they induced higher likelihood of wintertime flooding and reduced runoff and soil moisture in the summer. Changes in surface water and energy budgets in the CRB and SSJ basin were affected mainly by changes in surface temperature, which were statistically significant at the 0.95 confidence level. Changes in precipitation, while spatially incoherent, were not statistically significant except for the drying trend during summer. Because snow and runoff are highly sensitive tospatial distributions of temperature and precipitation, this study shows that (1) downscaling provides more realistic estimates of hydrologic impacts in mountainous regions such as the western U.S., and (2) despite relatively small changes in temperature and precipitation, changes in snowpack and runoff can be much larger on monthly to seasonal time scales because the effects of temperature and precipitation are integrated over time and space through various surface hydrological and land-atmosphere feedback processes. Although the results reported in this study were derived from an ensemble of regional climate simulations driven by a global climate model that displays low climate sensitivity compared with most other models, climate change was found to significantly affect water resources in the western U.S. by the mid twenty-first century.

Synthesis of colloidal Mn2+:ZnO quantum dots and high-TC ferromagnetic nanocrystalline thin films

Abstract: We report the synthesis of colloidal Mn(2+)-doped ZnO (Mn(2+):ZnO) quantum dots and the preparation of room-temperature ferromagnetic nanocrystalline thin films. Mn(2+):ZnO nanocrystals were prepared by a hydrolysis and condensation reaction in DMSO under atmospheric conditions. Synthesis was monitored by electronic absorption and electron paramagnetic resonance (EPR) spectroscopies. Zn(OAc)(2) was found to strongly inhibit oxidation of Mn(2+) by O(2), allowing the synthesis of Mn(2+):ZnO to be performed aerobically. Mn(2+) ions were removed from the surfaces of as-prepared nanocrystals using dodecylamine to yield high-quality internally doped Mn(2+):ZnO colloids of nearly spherical shape and uniform diameter (6.1 +/- 0.7 nm). Simulations of the highly resolved X- and Q-band nanocrystal EPR spectra, combined with quantitative analysis of magnetic susceptibilities, confirmed that the manganese is substitutionally incorporated into the ZnO nanocrystals as Mn(2+) with very homogeneous speciation, differing from bulk Mn(2+):ZnO only in the magnitude of D-strain. Robust ferromagnetism was observed in spin-coated thin films of the nanocrystals, with 300 K saturation moments as large as 1.35 micro(B)/Mn(2+) and T(C) > 350 K. A distinct ferromagnetic resonance signal was observed in the EPR spectra of the ferromagnetic films. The occurrence of ferromagnetism in Mn(2+):ZnO and its dependence on synthetic variables are discussed in the context of these and previous theoretical and experimental results.

Protein immobilization on carbon nanotubes via a two-step process of diimide-activated amidation

Abstract: Ferritin and bovine serum albumin (BSA) proteins are chemically bonded to nitrogen-doped multi-walled carbon nanotubes (CNx MWNTs) through a two-step process of diimide-activated amidation. First, carboxylated CNx MWNTs were activated by N-ethyl-N′-(3-dimethylaminopropyl)carbodiimide hydrochloride (EDAC), forming a stable active ester in the presence of N-hydroxysuccinimide (NHS). Second, the active ester was reacted with the amine groups on the proteins of ferritin or BSA, forming an amide bond between the CNx MWNTs and proteins. This two-step process avoids the intermolecular conjugation of proteins, and guarantees the uniform attachment of proteins on carbon nanotubes. TEM and AFM measurements clearly confirmed the successful attachment. This approach provides a universal and efficient method to attach biomolecules to carbon nanotubes at ambient conditions.

Synthesis of Colloidal Mn2+:ZnO Quantum Dots and High-TC Ferromagnetic Nanocrystalline Thin Films

Abstract: We report the synthesis of colloidal Mn2+-doped ZnO (Mn2+:ZnO) quantum dots and the preparation of room-temperature ferromagnetic nanocrystalline thin films. Mn2+:ZnO nanocrystals were prepared by a hydrolysis and condensation reaction in DMSO under atmospheric conditions. Synthesis was monitored by electronic absorption and electron paramagnetic resonance (EPR) spectroscopies. Zn(OAc)2 was found to strongly inhibit oxidation of Mn2+ by O2, allowing the synthesis of Mn2+:ZnO to be performed aerobically. Mn2+ ions were removed from the surfaces of as-prepared nanocrystals using dodecylamine to yield high-quality internally doped Mn2+:ZnO colloids of nearly spherical shape and uniform diameter (6.1 +/- 0.7 nm). Simulations of the highly resolved X- and Q-band nanocrystal EPR spectra, combined with quantitative analysis of magnetic susceptibilities, confirmed that the manganese is substitutionally incorporated into the ZnO nanocrystals as Mn2+ with very homogeneous speciation, differing from bulk Mn2+:ZnO only in the magnitude of D-strain. Robust ferromagnetism was observed in spin-coated thin films of the nanocrystals, with 300 K saturation moments as large as 1.35 Bohr magneton/Mn2+ and TC > 350 K. A distinct ferromagnetic resonance signal was observed in the EPR spectra of the ferromagnetic films. The occurrence of ferromagnetism in Mn2+:ZnO and its dependence on synthetic variables are discussed in the context of these and previous theoretical and experimental results.

The Effects of Climate Change on Water Resources in the West: Introduction and Overview

Abstract: The results of an experimental 'end to end' assessment of the effects of climate change on water resources in the western United States are described. The assessment focuses on the potential effects of climate change over the first half of the 21st century on the Columbia, Sacramento/San Joaquin, and Colorado river basins. The paper describes the methodology used for the assessment, and it summarizes the principal findings of the study. The strengths and weaknesses of this study are discussed, and suggestions are made for improving future climate change assessments. In the summer of 2000, the U.S. Department of Energy (DOE) funded a project to perform an experimental 'end-to-end' assessment of the effects of climate change on the western United States. The project was intended both to demonstrate and test a methodology for performing quantitative assessments of climate-driven environ- mental impacts. A second objective was to provide useful information to regional, state, and local decision-makers, whose job it will be to deal with the conflict- ing demands that climate change, population increases, and economic growth will place on the water resources of the West. The third objective was to demonstrate the potential value of an Accelerated Climate Prediction Initiative (ACPI). The ACPI was a DOE initiative to accelerate the development, improvement, and application of U.S. climate models and to provide the advanced computational facilities that would be needed to carry out this work. Although the ACPI was not funded, some of its spirit lives on in various DOE and other federal agency projects and programs designed to advance 'ultra-scale' computing and the science of climate simulation. In this volume, we hope to demonstrate what can be achieved if a highly qualified group of scientists are brought together, under relatively light management reins, to take an in-depth look at how future climate change might affect issues of real importance to the citizens of the United States. Other assessments have been made of the potential effects of climate change on the West (National Assessment Report, 2000), but this current work differs from previous assessments in important ways. The principal differences are as follows:

Geomicrobiology of High-Level Nuclear Waste-Contaminated Vadose Sediments at the Hanford Site, Washington State

Abstract: Sediments from a high-level nuclear waste plume were collected as part of investigations to evaluate the potential fate and migration of contaminants in the subsurface. The plume originated from a leak that occurred in 1962 from a waste tank consisting of high concentrations of alkali, nitrate, aluminate, Cr(VI), 137Cs, and 99Tc. Investigations were initiated to determine the distribution of viable microorganisms in the vadose sediment samples, probe the phylogeny of cultivated and uncultivated members, and evaluate the ability of the cultivated organisms to survive acute doses of ionizing radiation. The populations of viable aerobic heterotrophic bacteria were generally low, from below detection to ∼104 CFU g−1, but viable microorganisms were recovered from 11 of 16 samples, including several of the most radioactive ones (e.g., >10 μCi of 137Cs/g). The isolates from the contaminated sediments and clone libraries from sediment DNA extracts were dominated by members related to known gram-positive bacteria. Gram-positive bacteria most closely related to Arthrobacter species were the most common isolates among all samples, but other phyla high in G+C content were also represented, including Rhodococcus and Nocardia. Two isolates from the second-most radioactive sample (>20 μCi of 137Cs g−1) were closely related to Deinococcus radiodurans and were able to survive acute doses of ionizing radiation approaching 20 kGy. Many of the gram-positive isolates were resistant to lower levels of gamma radiation. These results demonstrate that gram-positive bacteria, predominantly from phyla high in G+C content, are indigenous to Hanford vadose sediments and that some are effective at surviving the extreme physical and chemical stress associated with radioactive waste.

Ions at the Air/Water Interface

Abstract: Thermodynamic analysis suggests that ions tend to be excluded from the air/water interface in simple salt solutions. In his Perspective, Garrett reviews recent molecular dynamics simulations and experimental studies that provide evidence to the contrary: Ions are found at the interface, sometimes even at enhanced concentrations. The author explains how this new picture may be reconciled with the thermodynamic observations. Ions in the surface layer are likely to play an important role in atmospheric reactions involving aerosol particles.

Ultra-High-Efficiency Strong Cation Exchange LC/RPLC/MS/MS for High Dynamic Range Characterization of the Human Plasma Proteome

Abstract: High-efficiency nanoscale reversed-phase liquid chromatography (chromatographic peak capacities of ∼1000: Shen, Y.; Zhao, R.; Berger, S. J.; Anderson, G. A.; Rodriguez, N.; Smith, R. D. Anal. Chem. 2002, 74, 4235. Shen, Y.; Moore, R. J.; Zhao, R.; Blonder, J.; Auberry, D. L.; Masselon, C.; Pasa-Tolic, L.; Hixson, K. K.; Auberry, K. J.; Smith, R. D. Anal. Chem. 2003, 75, 3596.) and strong cation exchange LC was used to obtain ultra-high-efficiency separations (combined chromatographic peak capacities of >104) in conjunction with tandem mass spectrometry (MS/MS) for characterization of the human plasma proteome. Using conservative SEQUEST peptide identification criteria (i.e., without considering chymotryptic or elastic peptides) and peptide LC normalized elution time constraints, the separation quality enabled the identification of proteins over a dynamic range of greater than 8 orders of magnitude in relative abundance using ion trap MS/MS instrumentation. Between 800 and 1682 human proteins were identif...

Disposable Carbon Nanotube Modified Screen‐Printed Biosensor for Amperometric Detection of Organophosphorus Pesticides and Nerve Agents

Abstract: A disposable carbon nanotube-based biosensor was successfully developed and applied to the detection of organophosphorus (OP) pesticides and nerve agents The biosensors using acetycholinesterase (AChE)/choline oxidase (CHO) enzymes provided a high sensitivity, large linear range, and low detection limits for the analysis of OP compounds Such characteristics may be attributed to the catalytic activity of carbon nanotube to promote the redox reaction of hydrogen peroxide produced during AChE/CHO enzymatic reactions with their substrate, as well as the large surface area of carbon nanotube materials

MIRAGE: Model description and evaluation of aerosols and trace gases

Abstract: [1] The Model for Integrated Research on Atmospheric Global Exchanges (MIRAGE) modeling system, designed to study the impacts of anthropogenic aerosols on the global environment, is described. MIRAGE consists of a chemical transport model coupled online with a global climate model. The chemical transport model simulates trace gases, aerosol number, and aerosol chemical component mass (sulfate, methane sulfonic acid (MSA), organic matter, black carbon (BC), sea salt, and mineral dust) for four aerosol modes (Aitken, accumulation, coarse sea salt, and coarse mineral dust) using the modal aerosol dynamics approach. Cloud-phase and interstitial aerosol are predicted separately. The climate model, based on Community Climate Model, Version 2 (CCM2), has physically based treatments of aerosol direct and indirect forcing. Stratiform cloud water and droplet number are simulated using a bulk microphysics parameterization that includes aerosol activation. Aerosol and trace gas species simulated by MIRAGE are presented and evaluated using surface and aircraft measurements. Surface-level SO2 in North American and European source regions is higher than observed. SO2 above the boundary layer is in better agreement with observations, and surface-level SO2 at marine locations is somewhat lower than observed. Comparison with other models suggests insufficient SO2 dry deposition; increasing the deposition velocity improves simulated SO2. Surface-level sulfate in North American and European source regions is in good agreement with observations, although the seasonal cycle in Europe is stronger than observed. Surface-level sulfate at high-latitude and marine locations, and sulfate above the boundary layer, are higher than observed. This is attributed primarily to insufficient wet removal; increasing the wet removal improves simulated sulfate at remote locations and aloft. Because of the high sulfate bias, radiative forcing estimates for anthropogenic sulfur given in 2001 by S. J. Ghan and colleagues are probably too high. Surface-level dimethyl sulfide (DMS) is ∼40% higher than observed, and the seasonal cycle shows too much DMS in local winter, partially caused by neglect of oxidation by NO3. Surface-level MSA at marine locations is ∼80% higher than observed, also attributed to insufficient wet removal. Surface-level BC is ∼50% lower than observed in the United States and ∼40% lower than observed globally. Treating BC as initially hydrophobic would lessen this bias. Surface-level organic matter is lower than observed in the United States, similar to BC, but shows no bias in the global comparison. Surface-level sea salt concentrations are ∼30% lower than observed, partly caused by low temporal variance of the model's 10 m wind speeds. Submicrometer sea salt is strongly underestimated by the emissions parameterization. Dust concentrations are within a factor of 3 at most sites but tend to be lower than observed, primarily because of neglect of very large particles and underestimation of emissions and vertical transport under high-wind conditions. Accumulation and Aitken mode number concentrations and mean sizes at the surface over ocean, and condensation nuclei concentrations aloft over the Pacific, are in fair agreement with observations. Concentrations over land are generally higher than observations, with mean sizes correspondingly lower than observations, especially at some European locations. Increasing the assumed size of emitted particles produces better agreement at the surface over land, and reducing the particle nucleation rate improves the agreement aloft over land.

Visual Analytics

Abstract: The information revolution is upon us, and it is guaran-teed to change our lives and the way we conduct our daily business. The fact that we have to deal with not just the size but also the variety and complexity of this in-formation makes it a real challenge to survive the revolu-tion. Enter Visual Analytics, a contemporary and proven approach to combine the art of human intuition and the science of mathematical deduction to directly perceive patterns and derive knowledge and insight from them.

A state-queueing model of thermostatically controlled appliances

Abstract: This paper develops a state-queueing model to analyze the price response of aggregated loads consisting of thermostatically controlled appliances (TCAs). Assuming a perfectly diversified load before the price response, we show that TCA setpoint changes in response to the market price will result in a redistribution of TCAs in on/off states and therefore change the probabilities for a unit to reside in each state. A randomly distributed load can be partially synchronized and the aggregated diversity lost. The loss of the load diversity can then create unexpected dynamics in the aggregated load profile. Raising issues such as restoring load diversity and damping the peak loads are also addressed in this paper.

Apparent decreases in colloid deposition rate coefficients with distance of transport under unfavorable deposition conditions: a general phenomenon.

Abstract: The transport of polystyrene microspheres was examined in packed glass beads under a variety of environmentally relevant ionic strength and flow conditions. The observed profiles of numbers of retained microspheres versus distance from the column entrance were much steeper than expected based on a constant rate coefficient of deposition acrossthe length of the column, indicating apparent decreases in deposition rate coefficients with transport distance. Deviation in the profile from log-linear decreases with distance was greatest under highly unfavorable conditions (low ionic strength), relatively reduced under mildly unfavorable conditions (high ionic strength), and was eliminated under favorable conditions. The generality of apparent decreases in deposition rate coefficients with distance of transport among microspheres, bacteria, and viruses leads to the conclusion that such effects reflect processes that are fundamental to filtration under unfavorable conditions. Numerical simulations of experiments that were performed under unfavorable conditions utilized a log-normal distribution of deposition rate coefficients among the colloid population in orderto simulate the effluent curves and retained profiles simultaneously. It is shown that while straining could be a significant contributor to the steep retained profiles at low ionic strength, where overall retention is low, distribution in interaction potentials among the population was a viable mechanism that can yield apparent decreases in deposition rate coefficients with distance of transport.

Supercritical fluid synthesis and characterization of catalytic metal nanoparticles on carbon nanotubes

Abstract: A rapid, convenient and environmentally benign method has been developed for the fabrication of metal nanoparticle–multiwall carbon nanotube (MWCNT) composites. Nanoparticles of palladium, rhodium and ruthenium are deposited onto functionalized MWCNTs through a simple hydrogen reduction of metal–β-diketone precursors in supercritical carbon dioxide, and are characterized by transmission electron microscopy (TEM), energy dispersive X-ray spectroscopy (EDS) and X-ray photoelectron spectroscopy (XPS) analyses. These highly dispersed nanoparticles, with a narrow range of size distribution and good adhesion on MWCNT surfaces, are expected to exhibit promising catalytic properties for a variety of chemical reactions. Preliminary experiments demonstrate that Pd nanoparticles supported on MWCNTs are effective catalysts for hydrogenation of olefins in carbon dioxide. The Pd nanoparticle–MWCNT composite also shows a high electrocatalytic activity in oxygen reduction for potential fuel cell application.

Strong Room-Temperature Ferromagnetism in Co2+-Doped TiO2 Made from Colloidal Nanocrystals

Abstract: Colloidal cobalt-doped TiO2 (anatase) nanocrystals were synthesized and studied by electronic absorption, magnetic circular dichroism, transmission electron microscopy, magnetic susceptibility, cobalt K-shell X-ray absorption spectroscopy, and extended X-ray absorption fine structure measurements. The nanocrystals were paramagnetic when isolated by surface-passivating ligands, weakly ferromagnetic (Ms ≈ 1.5 × 10-3 μB/Co2+ at 300 K) when aggregated, and strongly ferromagnetic (up to Ms = 1.9 μB/Co2+ at 300 K) when spin-coated into nanocrystalline films. X-ray absorption data reveal that cobalt is in the Co2+ oxidation state in all samples. In addition to providing strong experimental support for the existence of intrinsic ferromagnetism in cobalt-doped TiO2, these results demonstrate the possibility of using colloidal TiO2 diluted magnetic semiconductor nanocrystals as building blocks for assembly of ferromagnetic semiconductor nanostructures with potential spintronics applications.

Maximum likelihood Bayesian averaging of spatial variability models in unsaturated fractured tuff

Abstract: [1] Hydrologic analyses typically rely on a single conceptual-mathematical model. Yet hydrologic environments are open and complex, rendering them prone to multiple interpretations and mathematical descriptions. Adopting only one of these may lead to statistical bias and underestimation of uncertainty. Bayesian model averaging (BMA) [Hoeting et al., 1999] provides an optimal way to combine the predictions of several competing models and to assess their joint predictive uncertainty. However, it tends to be computationally demanding and relies heavily on prior information about model parameters. Neuman [2002, 2003] proposed a maximum likelihood version (MLBMA) of BMA to render it computationally feasible and to allow dealing with cases where reliable prior information is lacking. We apply MLBMA to seven alternative variogram models of log air permeability data from single-hole pneumatic injection tests in six boreholes at the Apache Leap Research Site (ALRS) in central Arizona. Unbiased ML estimates of variogram and drift parameters are obtained using adjoint state maximum likelihood cross validation [Samper and Neuman, 1989a] in conjunction with universal kriging and generalized least squares. Standard information criteria provide an ambiguous ranking of the models, which does not justify selecting one of them and discarding all others as is commonly done in practice. Instead, we eliminate some of the models based on their negligibly small posterior probabilities and use the rest to project the measured log permeabilities by kriging onto a rock volume containing the six boreholes. We then average these four projections and associated kriging variances, using the posterior probability of each model as weight. Finally, we cross validate the results by eliminating from consideration all data from one borehole at a time, repeating the above process and comparing the predictive capability of MLBMA with that of each individual model. We find that MLBMA is superior to any individual geostatistical model of log permeability among those we consider at the ALRS.