Showing papers by "Pacific Northwest National Laboratory published in 2000"

Remediation of Cr(VI) and Pb(II) aqueous solutions using supported, nanoscale zero-valent iron

Abstract: Borohydride reduction of an aqueous iron salt in the presence of a support material gives supported zero-valent iron nanoparticles that are 10−30 nm in diameter. The material is stable in air once it has dried and contains 22.6% iron by weight. The supported zero-valent iron nanoparticles (“Ferragels”) rapidly separate and immobilize Cr(VI) and Pb(II) from aqueous solution, reducing the chromium to Cr(III) and the Pb to Pb(0) while oxidizing the Fe to goethite (α-FeOOH). The kinetics of the reduction reactions are complex and include an adsorption phase. About 10% of the iron in the material appears to be located at active surface sites. Once these sites have been saturated, the reduction process continues but at a much lower rate, which is likely limited by mass transfer. Rates of remediation of Cr(VI) and Pb(II) are up to 30 times higher for Ferragels than for iron filings or iron powder on a (Fe) molar basis. Over 2 months, reduction of Cr(VI) was 4.8 times greater for Ferragels than for an equal weigh...

Surfactant-assisted processing of carbon nanotube/polymer composites

Abstract: Interfacial interaction is one of the most critical issues in carbon nanotube/polymer composites In this paper the role of nonionic surfactant is investigated With the surfactant as the processing aid, the addition of only 1 wt % carbon nanotubes in the composite increases the glass transition temperature from 63 °C to 88 °C The elastic modulus is also increased by more than 30% In contrast, the addition of carbon nanotubes without the surfactant only has moderate effects on the glass transition temperature and on the mechanical properties This work points to the pathways to improve dispersion and to modify interfacial bonding in carbon nanotube/polymer composites

Production of levulinic acid and use as a platform chemical for derived products

Abstract: Levulinic acid (LA) can be produced cost effectively and in high yield from renewable feedstocks in a new industrial process. The technology is being demonstrated on a 1 ton/day scale at a facility in South Glens Falls, New York. Low cost LA can be used as a platform chemical for the production of a wide range of value-added products. This research has demonstrated that LA can be converted to methyltetrahydrofuran (MTHF), a solvent and fuel extender. MTHF is produced in >80% molar yield via a single stage catalytic hydrogenation process. A new preparation of δ-aminolevulinic acid (DALA), a broad spectrum herbicide, from LA has also been developed. Each step in this new process proceeds in high (>80%) yield and affords DALA (as the hydrochloride salt) in >90% purity, giving a process that could be commercially viable. LA is also being investigated as a starting material for the production of diphenolic acid (DPA), a direct replacement for bisphenol A.

Suppliers and Environmental Innovation: The Automotive Paint Process

Abstract: Automobile assembly plants worldwide face increasing pressures in the environmental arena. How a plant responds to these issues has significant implications for the cost and quality of plant operations. This paper uses three case studies of US assembly plants to examine the role of partnerships between original equipment manufacturers (OEMs) and their suppliers in improving the environmental performance of manufacturing operations. We find that strong partnerships with suppliers, supported by appropriate incentive systems, were a significant element of the successful application of innovative environmental technologies. Supplier staff members were an important part of achieving environmental performance improvements while maintaining production quality and cost goals. The management factors influencing the extent and nature of supplier involvement are identified. The results of this work point to the importance of suppliers in addressing the manufacturing challenges of the future.

ThemeRiver: visualizing theme changes over time

Abstract: ThemeRiver/sup TM/ is a prototype system that visualizes thematic variations over time within a large collection of documents. The "river" flows from left to right through time, changing width to depict changes in thematic strength of temporally associated documents. Colored "currents" flowing within the river narrow or widen to indicate decreases or increases in the strength of an individual topic or a group of topics in the associated documents. The river is shown within the context of a timeline and a corresponding textual presentation of external events.

Models and mechanisms of irradiation-induced amorphization in ceramics

Abstract: A number of models have been developed to describe the various amorphization processes and the effects of temperature on the kinetics of amorphization. These models are reviewed and in some cases further developed. In general, these models contain a number of parameters relating to irradiation-assisted and thermal recovery processes, which make their application to existing data sets challenging. Nonetheless, general aspects of the models yield insights into the rate-limiting processes controlling the kinetics of amorphization within a given temperature regime. Several examples are used to illustrate features of the models and to highlight differences in behavior.

LDA and GGA calculations for high-pressure phase transitions in ZnO and MgO

Abstract: We report total energy and electronic structure calculations for ZnO in the B4 (wurtzite), B3 (zinc blende), B1 (rocksalt), and B2 (CsCl) crystal structures over a range of unit cell volumes. We employed both the local-density approximation (LDA) and the PBE96 form of the generalized gradient approximation (GGA) together with optimized Gaussian basis sets to expand the crystal orbitals and periodic electron density. In agreement with earlier ab initio calculations and with experiment, we find that the B4 phase of ZnO is slightly lower in energy than the B3 phase, and that it transforms first to the B1 structure under applied pressure. The equilibrium transition pressure ${p}_{T1}$ is 6.6 GPa at the LDA level of theory and 9.3 GPa in the GGA, compared to experimental values around 9 GPa. This confirms a trend seen by other workers in which the LDA underestimates structural transition pressures which are more accurately predicted by the GGA. At much higher compression, we predict that the B1 phase of ZnO will transform to the B2 (cesium chloride) structure at ${p}_{T2}=260\mathrm{GPa}$ (LDA) or 256 GPa (GGA) indicating that gradient corrections are small for this material at megabar pressures. This is the first quantitative prediction of this transition in ZnO, and should be testable with diamond-anvil techniques. We predict that ZnO remains a semiconductor up to ${p}_{T2}.$ For comparison we find that the B1 to B2 transition in MgO occurs at 515 GPa with either LDA or GGA, in excellent agreement with other ab initio predictions.

Engineering Deinococcus radiodurans for metal remediation in radioactive mixed waste environments.

Abstract: We have developed a radiation resistant bacterium for the treatment of mixed radioactive wastes containing ionic mercury. The high cost of remediating radioactive waste sites from nuclear weapons production has stimulated the development of bioremediation strategies using Deinococcus radiodurans, the most radiation resistant organism known. As a frequent constituent of these sites is the highly toxic ionic mercury (Hg) (II), we have generated several D. radiodurans strains expressing the cloned Hg (II) resistance gene (merA) from Escherichia coli strain BL308. We designed four different expression vectors for this purpose, and compared the relative advantages of each. The strains were shown to grow in the presence of both radiation and ionic mercury at concentrations well above those found in radioactive waste sites, and to effectively reduce Hg (II) to the less toxic volatile elemental mercury. We also demonstrated that different gene clusters could be used to engineer D. radiodurans for treatment of mixed radioactive wastes by developing a strain to detoxify both mercury and toluene. These expression systems could provide models to guide future D. radiodurans engineering efforts aimed at integrating several remediation functions into a single host.

Dechlorination of Carbon Tetrachloride by Fe(II) Associated with Goethite

Abstract: Carbon tetrachloride (CT) was dechlorinated to chloroform (CF) under anoxic conditions by Fe(II) that was sorbed to the surface of goethite (α-FeOOH). No reaction occurred when Fe(II) was present and goethite was absent. Several abiotic experiments were conducted with goethite at 30 °C in which the total amount of Fe(II) in the system, the amount of sorbed Fe(II), the density of sorbed Fe(II), and the pH were varied. Regeneration of sorbed Fe(II) occurred when dissolved Fe2+ was available and maintained pseudo-first-order conditions with respect to CT. Analysis of the rates of CT loss for experiments with sorbed-Fe(II) regeneration showed the rate-determining-step to be first order with respect to CT, second order with respect to the volumetric concentration of sorbed Fe(II) (i.e., mmol sorbed Fe(II) L-1 suspension), and zero order with respect to H+ for pH between 4.2 and 7.3. The absolute rate constant for the reaction was determined to be 42 ± 5 M-2 s-1. Normalization of the observed rate constants to ...

Trichloroethene Reductive Dehalogenase from Dehalococcoides ethenogenes: Sequence of tceA and Substrate Range Characterization

Abstract: The anaerobic bacterium Dehalococcoides ethenogenes is the only known organism that can completely dechlorinate tetrachloroethene or trichloroethene (TCE) to ethene via dehalorespiration. One of two corrinoid-containing enzymes responsible for this pathway, TCE reductive dehalogenase (TCE-RDase) catalyzes the dechlorination of TCE to ethene. TCE-RDase dehalogenated 1,2-dichloroethane and 1, 2-dibromoethane to ethene at rates of 7.5 and 30 micromol/min/mg, respectively, similar to the rates for TCE, cis-dichloroethene (DCE), and 1,1-DCE. A variety of other haloalkanes and haloalkenes containing three to five carbon atoms were dehalogenated at lower rates. The gene encoding TCE-RDase, tceA, was cloned and sequenced via an inverse PCR approach. Sequence comparisons of tceA to proteins in the public databases revealed weak sequence similarity confined to the C-terminal region, which contains the eight-iron ferredoxin cluster binding motif, (CXXCXXCXXXCP)(2). Direct N-terminal sequencing of the mature enzyme indicated that the first 42 amino acids constitute a signal sequence containing the twin-arginine motif, RRXFXK, associated with the Sec-independent membrane translocation system. This information coupled with membrane localization studies indicated that TCE-RDase is located on the exterior of the cytoplasmic membrane. Like the case for the two other RDases that have been cloned and sequenced, a small open reading frame, tceB, is proposed to be involved with membrane association of TCE-RDase and is predicted to be cotranscribed with tceA.

Reduction of Fe(III), Cr(VI), U(VI), and Tc(VII) by Deinococcus radiodurans R1

Abstract: Deinococcus radiodurans is an exceptionally radiation-resistant microorganism capable of surviving acute exposures to ionizing radiation doses of 15,000 Gy and previously described as having a strictly aerobic respiratory metabolism. Under strict anaerobic conditions, D. radiodurans R1 reduced Fe(III)-nitrilotriacetic acid coupled to the oxidation of lactate to CO(2) and acetate but was unable to link this process to growth. D. radiodurans reduced the humic acid analog anthraquinone-2,6-disulfonate (AQDS) to its dihydroquinone form, AH(2)DS, which subsequently transferred electrons to the Fe(III) oxides hydrous ferric oxide and goethite via a previously described electron shuttle mechanism. D. radiodurans reduced the solid-phase Fe(III) oxides in the presence of either 0.1 mM AQDS or leonardite humic acids (2 mg ml(-1)) but not in their absence. D. radiodurans also reduced U(VI) and Tc(VII) in the presence of AQDS. In contrast, Cr(VI) was directly reduced in anaerobic cultures with lactate although the rate of reduction was higher in the presence of AQDS. The results are the first evidence that D. radiodurans can reduce Fe(III) coupled to the oxidation of lactate or other organic compounds. Also, D. radiodurans, in combination with humic acids or synthetic electron shuttle agents, can reduce U and Tc and thus has potential applications for remediation of metal- and radionuclide-contaminated sites where ionizing radiation or other DNA-damaging agents may restrict the activity of more sensitive organisms.

The fall, recovery, orbit, and composition of the Tagish Lake meteorite: a new type of carbonaceous chondrite.

Abstract: The preatmospheric mass of the Tagish Lake meteoroid was about 200,000 kilograms. Its calculated orbit indicates affinity to the Apollo asteroids with a semimajor axis in the middle of the asteroid belt, consistent with a linkage to low-albedo C, D, and P type asteroids. The mineralogy, oxygen isotope, and bulk chemical composition of recovered samples of the Tagish Lake meteorite are intermediate between CM and CI meteorites. These data suggest that the Tagish Lake meteorite may be one of the most primitive solar system materials yet studied.

Utility of accurate mass tags for proteome-wide protein identification.

Abstract: An enabling capability for proteomics would be the ability to study protein expression on a global scale. While several different separation and analysis options are being investigated to advance the practice of proteomics, mass spectrometry (MS) is rapidly becoming the core instrumental technology used to characterize the large number of proteins that constitute a proteome. To be most effective, proteomic measurements must be high-throughput, ideally allowing thousands of proteins to be identified on a time scale of hours. Most strategies of identification by MS rely on the analysis of enzymatically produced peptides originating from an isolated protein followed by either peptide mapping or tandem MS (MS/MS) to obtain sequence information for a single peptide. In the case of peptide mapping, several peptide masses are needed to unambiguously identify a protein with the typically achieved mass measurement accuracies (MMA). The ability to identify proteins based on the mass of a single peptide (i.e., an accurate mass tag; AMT) is proposed and is largely dependent on the MMA that can be achieved. To determine the MMA necessary to enable the use of AMTs for proteome-wide protein identification, we analyzed the predicted proteins and their tryptic fragments from Saccharomyces cerevisiae and Caenorhabditis elegans. The results show that low ppm (i.e., approximately 1 ppm) level measurements have practical utility for analysis of small proteomes. Additionally, up to 85% of the peptides predicted from these organisms can function as AMTs at sub-ppm MMA levels attainable using Fourier transform ion cyclotron resonance MS. Additional information, such as sequence constraints, should enable even more complex proteomes to be studied at more modest mass measurement accuracies. Once AMTs are established, subsequent high-throughput measurements of proteomes (e.g., after perturbations) will be greatly facilitated.

An algorithm for automated bacterial identification using matrix-assisted laser desorption/ionization mass spectrometry.

Abstract: An algorithm for bacterial identification using matrix-assisted laser desorption/ionization (MALDI) mass spectrometry is being developed. This mass spectral fingerprint comparison algorithm is fully automated and statistically based, providing objective analysis of samples to be identified. Based on extraction of reference fingerprint ions from test spectra, this approach should lend itself well to real-world applications where samples are likely to be impure. This algorithm is illustrated using a blind study. In the study, MALDI-MS fingerprints for Bacillus atrophaeus ATCC 49337, Bacillus cereus ATCC 14579T, Escherichia coli ATCC 33694, Pantoea agglomerans ATCC 33243, and Pseudomonas putida F1 are collected and form a reference library. The identification of test samples containing one or more reference bacteria, potentially mixed with one species not in the library (Shewanella alga BrY), is performed by comparison to the reference library with a calculated degree of association. Out of 60 samples, no fa...

Pressure drop measurements in a microchannel

Abstract: Recent developments in micro-energy and micro-chemical systems have produced a need for greater understanding of flow in small channels. Several recent studies of friction factors and transition Reynolds numbers in rectangular microchannels have produced results that differ from classical theory. In this work, friction factors and laminar flow friction constants were determined for water flowing in high aspect ratio channels with depths ranging from 128 to 521 μm. Reynolds numbers were between 60 and 3,450. Pressure drops were measured within the channel itself to exclude entrance and exit losses. Transitions to turbulence were observed with flow visualization. Uncertainties in measured variables were quantified and propagated into the estimated friction constants. Friction factors were also determined in a 1,050- μm-deep channel that served as a control. After considering experimental uncertainties and systematic errors, significant differences remained between the results and classical theory

Modeling microbial processes in porous media

Abstract: The incorporation of microbial processes into reactive transport models has generally proceeded along two separate lines of investigation: (1) transport of bacteria as inert colloids in porous media, and (2) the biodegradation of dissolved contaminants by a stationary phase of bacteria. Research over the last decade has indicated that these processes are closely linked. This linkage may occur when a change in metabolic activity alters the attachment/detachment rates of bacteria to surfaces, either promoting or retarding bacterial transport in a groundwater-contaminant plume. Changes in metabolic activity, in turn, are controlled by the time of exposure of the microbes to electron acceptors/donor and other components affecting activity. Similarly, metabolic activity can affect the reversibility of attachment, depending on the residence time of active microbes. Thus, improvements in quantitative analysis of active subsurface biota necessitate direct linkages between substrate availability, metabolic activity, growth, and attachment/detachment rates. This linkage requires both a detailed understanding of the biological processes and robust quantitative representations of these processes that can be tested experimentally. This paper presents an overview of current approaches used to represent physicochemical and biological processes in porous media, along with new conceptual approaches that link metabolic activity with partitioning of the microorganism between the aqueous and solid phases.

Plutonium immobilization and radiation effects.

Abstract: In their report “Radiation tolerance of complex oxides” (4 Aug., p. [748][1]), Sickafus and colleagues note in the last paragraph “that compounds with the fluorite structure are especially stable in a displacive radiation damage environment,” and they propose that complex oxides that have a

Trans-Pacific Air Pollution

Abstract: It is increasingly recognized that air pollution is transported on mid-latitude westerly winds from Eurasia to the Pacific Ocean basin and across to North America. This trans-Pacific pollution reaches North America and may have substantial impacts on ecosystems and climate in the entire Pacific region. In their Perspective, Wilkening et al . report from a recent meeting where researchers attempted to synthesize and evaluate existing knowledge about trans-Pacific pollutant transport.

Thermogelling Biodegradable Polymers with Hydrophilic Backbones: PEG-g-PLGA

Abstract: The aqueous solutions of poly(ethylene glycol) grafted with poly(lactic acid-co-glycolic acid) flow freely at room temperature but form gels at higher temperature. The existence of micelles in water at low polymer concentration was confirmed by cryo-transmission electron microscopy and dye solubilization studies. The micellar diameter is about 9 nm, and the critical micelle concentration is in a range of 0.01−0.05 wt %. The critical gel concentration, above which a gel phase appears, was 16 wt %, and the sol-to-gel transition temperature was slightly affected by the concentration between 16 and 25 wt %. At sol-to-gel transition, viscosity and modulus increased abruptly, and 13C NMR showed molecular motion of hydrophilic poly(ethylene glycol) backbones decreased while that of hydrophobic poly(lactic acid-co-glycolic acid) side chains increased. The hydrogel of PEG-g-PLGA with hydrophilic backbones was transparent during degradation and remained a gel for 1 week, suggesting a promising material for short-te...

Effect of Electron Donor and Solution Chemistry on Products of Dissimilatory Reduction of Technetium by Shewanella putrefaciens

Abstract: To help provide a fundamental basis for use of microbial dissimilatory reduction processes in separating or immobilizing (99)Tc in waste or groundwaters, the effects of electron donor and the presence of the bicarbonate ion on the rate and extent of pertechnetate ion [Tc(VII)O(4)(-)] enzymatic reduction by the subsurface metal-reducing bacterium Shewanella putrefaciens CN32 were determined, and the forms of aqueous and solid-phase reduction products were evaluated through a combination of high-resolution transmission electron microscopy, X-ray absorption spectroscopy, and thermodynamic calculations. When H(2) served as the electron donor, dissolved Tc(VII) was rapidly reduced to amorphous Tc(IV) hydrous oxide, which was largely associated with the cell in unbuffered 0. 85% NaCl and with extracellular particulates (0.2 to 0.001 microm) in bicarbonate buffer. Cell-associated Tc was present principally in the periplasm and outside the outer membrane. The reduction rate was much lower when lactate was the electron donor, with extracellular Tc(IV) hydrous oxide the dominant solid-phase reduction product, but in bicarbonate systems much less Tc(IV) was associated directly with the cell and solid-phase Tc(IV) carbonate may have been present. In the presence of carbonate, soluble (<0.001 microm) electronegative, Tc(IV) carbonate complexes were also formed that exceeded Tc(VII)O(4)(-) in electrophoretic mobility. Thermodynamic calculations indicate that the dominant reduced Tc species identified in the experiments would be stable over a range of E(h) and pH conditions typical of natural waters. Thus, carbonate complexes may represent an important pathway for Tc transport in anaerobic subsurface environments, where it has generally been assumed that Tc mobility is controlled by low-solubility Tc(IV) hydrous oxide and adsorptive, aqueous Tc(IV) hydrolysis products.

Microfabricated isoelectric focusing device for direct electrospray ionization-mass spectrometry.

Abstract: A novel microfabricated device for isoelectric focusing (IEF) incorporating an optimized electrospray ionization (ESI) tip was constructed on polycarbonate plates using laser micromachining. The IEF microchip incorporated a separation channel (50 μ × 30 μ × 16 cm), three fluid connectors, and two buffer reservoirs. Electrical potentials used for IEF focusing and electrospray were applied through platinum electrodes placed in the buffer reservoirs, which were isolated from the separation channel by porous membranes. Direct ESI-mass spectrometry (MS) using electrosprays produced directly from a sharp emitter „tip” on the microchip was evaluated. The results indicated that this design can produce a stable electrospray and that performance was further improved and made more flexible with the assistance of a sheath gas and sheath liquid. Error analysis of the spectral data showed that the standard deviation in signal intensity for an analyte peak was less than ˜ 5% over 3 h. The production of stable electrosprays directly from microchip IEF device represents a step towards easily fabricated microanalytical devices. Microchannel IEF separations of protein mixtures were demonstrated for uncoated polycarbonate microchips. Direct microchannel IEF-ESI-MS was demonstrated using the microfabricated chip with an ion-trap mass spectrometer for characterization of protein mixtures.