In this paper, we compare constructed records of concentrations of black carbon (BC)--an indicator of anthropogenic aerosols--with observed surface temperature trends in California. Annual average BC concentrations in major air basins in California significantly decreased after about 1990, coincident with an observed statewide surface temperature increase. Seasonal aerosol concentration trends are consistent with observed seasonal temperature trends. These data suggest that the reduction in anthropogenic aerosol concentrations contributed to the observed surface temperature increase. Conversely, high aerosol concentrations may lower surface temperature and partially offset the temperature increase of greenhouse gases.

The siderophore enterobactin (Ent) is produced by enteric bacteria to mediate iron uptake. Ent scavenges iron and is taken up by the bacteria as the highly stable ferric complex [Fe{sup III}(Ent)]{sup 3-}. This complex is also a specific target of the mammalian innate immune system protein, Siderocalin (Scn), which acts as an anti-bacterial agent by specifically sequestering siderophores and their ferric complexes during infection. Recent literature suggesting that Scn may also be involved in cellular iron transport has increased the importance of understanding the mechanism of siderophore interception and clearance by Scn; Scn is observed to release iron in acidic endosomes and [Fe{sup III}(Ent)]{sup 3-} is known to undergo a change from catecholate to salicylate coordination in acidic conditions, which is predicted to be sterically incompatible with the Scn binding pocket (also referred to as the calyx). To investigate the interactions between the ferric Ent complex and Scn at different pH values, two recombinant forms of Scn with mutations in three residues lining the calyx were prepared: Scn-W79A/R81A and Scn-Y106F. Binding studies and crystal structures of the Scn-W79A/R81A:[Fe{sup III}(Ent)]{sup 3-} and Scn-Y106F:[Fe{sup III}(Ent)]{sup 3-} complexes confirm that such mutations do not affect the overall conformation of the protein but do …

In this work we report on thevacuum-ultraviolet (VUV) photoionization of small methanol and methanol-water clusters. Clusters of methanol with water are generated via co-expansion of the gas phase constituents in a continuous supersonic jet expansion of methanol and water seeded in Ar. The resulting clusters are investigated by single photon ionization with tunable vacuumultraviolet synchrotron radiation and mass analyzed using reflectron mass spectrometry. Protonated methanol clusters of the form (CH3OH)nH + (n=1-12) dominate the mass spectrum below the ionization energy of the methanol monomer. With an increase in water concentration, small amounts of mixed clusters of the form (CH3OH)n(H2O)H + (n=2-11) are detected. The only unprotonated species observed in this work are the methanol monomer and dimer. Appearance energies are obtained from the photoionization efficiency (PIE) curves for CH3OH +, (CH 3OH)2 +, (CH3OH)nH + (n=1-9), and (CH 3OH)n(H2O)H + (n=2-9 ) as a function of photon energy. With an increase in the water content in the molecular beam, there is an enhancement of photoionization intensity for methanol dimer and protonated methanol monomer at threshold. These results are compared and contrasted to previous experimental observations.

Progress in science often follows or parallels the development of new techniques. The optical microscope helped convert medicine and biology from a speculative activity in old times to today's sophisticated scientific disciplines. The telescope changed the study and interpretation of heavens from mythology to science. X-ray diffraction enabled the flourishing of solid state physics and materials science. The technique object of this review, Ambient Pressure Photoelectron Spectroscopy or APPES for short, has also the potential of producing dramatic changes in the study of liquid and solid surfaces, particularly in areas such as atmospheric, environment and catalysis sciences. APPES adds an important missing element to the host of techniques that give fundamental information, i.e., spectroscopy and microscopy, about surfaces in the presence of gases and vapors, as encountered in industrial catalysis and atmospheric environments. APPES brings electron spectroscopy into the realm of techniques that can be used in practical environments. Decades of surface science in ultra high vacuum (UHV) has shown the power of electron spectroscopy in its various manifestations. Their unique property is the extremely short elastic mean free path of electrons as they travel through condensed matter, of the order of a few atomic distances in the energy range …

Citric acid forms bidentate, tridentate, binuclear or polynuclear species with transition metals and actinides. Biodegradation of metal citrate complexes is influenced by the type of complex formed with metal ions. While bidentate complexes are readily biodegraded, tridentate, binuclear and polynuclear species are recalcitrant. Likewise certain transition metals and actinides are photochemically active in the presence of organic acids. Although the uranyl citrate complex is not biodegraded, in the presence of visible light it undergoes photochemical oxidation/reduction reactions which result in the precipitation of uranium as UO{sub 3} {center_dot} H{sub 2}O. Consequently, we developed a process where uranium is extracted from contaminated soils and wastes by citric acid. The citric-acid extract is subjected to biodegradation to recover the toxic metals, whereas uranyl citrate which is recalcitrant remains in solution. Photochemical degradation of the uranium citrate complex resulted in the precipitation of uranium. Thus the toxic metals and uranium in mixed waste are recovered in separate fractions for recycling or for disposal. The use of naturally-occurring compounds and the combined chemical and microbiological treatment process is more efficient than present methods and should result in considerable savings in cost.

Detailed chemical speciation of the dry residue particles from individual cloud droplets and interstitial aerosol collected during the Marine Stratus Experiment (MASE) was performed using a combination of complementary microanalysis techniques. Techniques include computer controlled scanning electron microscopy with energy dispersed analysis of X-rays (CCSEM/EDX), time-of-flight secondary ionization mass spectrometry (TOF-SIMS), and scanning transmission X-ray microscopy with near edge X-ray absorption fine structure spectroscopy (STXM/NEXAFS). Samples were collected at the ground site located in Point Reyes National Seashore, approximately 1 km from the coast. This manuscript focuses on the analysis of individual particles sampled from air masses that originated over the open ocean and then passed through the area of the California current located along the northern California coast. Based on composition, morphology, and chemical bonding information, two externally mixed, distinct classes of sulfur containing particles were identified: chemically modified (aged) sea salt particles and secondary formed sulfate particles. The results indicate substantial heterogeneous replacement of chloride by methanesulfonate (CH3SO3-) and non-sea salt sulfate (nss-SO42-) in sea-salt particles with characteristic ratios of nss-S/Na>0.10 and CH3SO3-/nss-SO42->0.6.

The Gamma-ray Large Area Space telescope (GLAST) is a gamma-ray satellite scheduled for launch in 2008. Before the assembly of the Tracker subsystem of the Large Area Telescope (LAT) science instrument of GLAST, every component (tray) and module (tower) has been subjected to extensive ground testing required to ensure successful launch and on-orbit operation. This paper describes the sequence and results of the environmental tests performed on an engineering model and all the flight hardware of the GLAST LAT Tracker. Environmental tests include vibration testing, thermal cycles and thermal-vacuum cycles of every tray and tower as well as the verification of their electrical performance.

We investigated ZnO(0001) single crystals annealed in high vacuum with respect to their magnetic properties and cluster formation tendency after implant-doping with Fe. While metallic Fe cluster formation is suppressed, no evidence for the relevance of the Fe magnetic moment to the observed ferromagnetism was found. The latter along with the cluster suppression is discussed with respect to defects in the ZnO host matrix, since the crystalline quality of the substrates was lowered due to the preparation as observed by x-ray diffraction.

Scanning tunneling microscopy (STM) was used to study the dissociative adsorption of H{sub 2} on Ru(001) near saturation coverage, when the number of residual hydrogen vacancies (i.e., unoccupied Ru sites) is small. We found that H{sub 2} dissociation takes place only on Ru sites where the metal atom is not bound to any H atom. Such active sites are formed when at least 3 H-vacancies aggregate by thermal diffusion. Sites formed by single H-vacancies or pairs of adjoining vacancies were found to be unreactive toward H{sub 2}. As a similar phenomenon was found previously on Pd(111), the present results indicate that the active sites for H2 dissociation share a common characteristic among catalytically active transition metals.

A detailed chemical kinetic mechanism has been developed to study the oxidation of the straight-chain isomers of hexene over a wide range of operating conditions. The main features of this detailed kinetic mechanism, which includes both high and low temperature reaction pathways, are presented and discussed with special emphasis on the main classes of reactions involved in alkene oxidation. Simulation results have been compared with experimental data over a wide range of operating conditions including shock tube, jet stirred reactor and rapid compression machine. The different reactivities of the three isomers have been successfully predicted by the model. Isomerization reactions of the hexenyl radicals were found to play a significant role in the chemistry and interactions of the three n-hexene isomers. A comparative reaction flux analysis is used to verify and discuss the fundamental role of the double bond position in the isomerization reactions of alkenyl radicals, as well as the impact of the allylic site in the low and high temperature mechanism of fuel oxidation.

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Sulphate-reducing bacteria are anaerobes readily found in oxic-anoxic interfaces. Multiple defence pathways against oxidative conditions were identified in these organisms and proposed to be differentially expressed under different concentrations of oxygen, contributing to their ability to survive oxic conditions. In this study, Desulfovibrio vulgaris Hildenborough cells were exposed to the highest concentration of oxygen that sulphate-reducing bacteria are likely to encounter in natural habitats, and the global transcriptomic response was determined. 307 genes were responsive, with cellular roles in energy metabolism, protein fate, cell envelope and regulatory functions, including multiple genes encoding heat shock proteins, peptidases and proteins with heat shock promoters. Of the oxygen reducing mechanisms of D. vulgaris only the periplasmic hydrogen-dependent mechanism is up-regulated, involving the [NiFeSe]hydrogenase, formate dehydrogenase(s) and the Hmc membrane complex. The oxidative defence response concentrates on damage repair by metal-free enzymes. These data, together with the down regulation of the Fur operon, which restricts the availability of iron, and the lack of response of the PerR operon, suggest that a major effect of this oxygen stress is the inactivation and/or degradation of multiple metalloproteins present in D. vulgaris as a consequence of oxidative damage to their metal clusters.

We give a representation of the parity-even part of the planar two-loop six-gluon MHV amplitude of N = 4 super-Yang-Mills theory, in terms of loop-momentum integrals with simple dual conformal properties. We evaluate the integrals numerically in order to test directly the ABDK/BDS all-loop ansatz for planar MHV amplitudes. We find that the ansatz requires an additive remainder function, in accord with previous indications from strong-coupling and Regge limits. The planar six-gluon amplitude can also be compared with the hexagonal Wilson loop computed by Drummond, Henn, Korchemsky and Sokatchev in arXiv:0803.1466 [hep-th]. After accounting for differing singularities and other constants independent of the kinematics, we find that the Wilson loop and MHV-amplitude remainders are identical, to within our numerical precision. This result provides non-trivial confirmation of a proposed n-point equivalence between Wilson loops and planar MHV amplitudes, and suggests that an additional mechanism besides dual conformal symmetry fixes their form at six points and beyond.

The indoor atmosphere is an ecological unit that impacts on public health. To investigate the composition of organisms in this space, we applied culture-independent approaches to microbes harvested from the air of two densely populated urban buildings, from which we analyzed 80 megabases genomic DNA sequence and 6000 16S rDNA clones. The air microbiota is primarily bacteria, including potential opportunistic pathogens commonly isolated from human-inhabited environments such as hospitals, but none of the data contain matches to virulent pathogens or bioterror agents. Comparison of air samples with each other and nearby environments suggested that the indoor air microbes are not random transients from surrounding outdoor environments, but rather originate from indoor niches. Sequence annotation by gene function revealed specific adaptive capabilities enriched in the air environment, including genes potentially involved in resistance to desiccation and oxidative damage. This baseline index of air microbiota will be valuable for improving designs of surveillance for natural or man-made release of virulent pathogens.

Various model equations are available for representing the excess Gibbs energy properties (osmotic and activity coefficients) of aqueous and other liquid mixed-electrolyte solutions. Scatchard's neutral-electrolyte model is among the simplest of these equations for ternary systems and contains terms that represent both symmetrical and asymmetric deviations from ideal mixing behavior when two single-electrolyte solutions are mixed in different proportions at constant ionic strengths. The usual form of this model allows from zero to six mixing parameters. In this report we present an analytical method for transforming the mixing parameters of neutral-electrolyte-type models with larger numbers of mixing parameters directly to those of models with fewer mixing parameters, without recourse to the source data used for evaluation of the original model parameters. The equations for this parameter conversion are based on an extension to ternary systems of the methodology of Rard and Wijesinghe [J. Chem. Thermodyn. 35, 439-473 (2003)] and Wijesinghe and Rard [J. Chem. Thermodyn. 37, 1196-1218 (2005)] that was applied by them to binary systems. It was found that the use of this approach with a constant ionic-strength cutoff of I {le} 6.2 mol {center_dot} kg{sup -1} (the NaCl solubility limit) yielded parameters for the NaCl + SrCl{sub 2} …

A procedure for carrying out iterative model-building, density modification and refinement is presented in which the density in an OMIT region is essentially unbiased by an atomic model. Density from a set of overlapping OMIT regions can be combined to create a composite 'Iterative-Build' OMIT map that is everywhere unbiased by an atomic model but also everywhere benefiting from the model-based information present elsewhere in the unit cell. The procedure may have applications in the validation of specific features in atomic models as well as in overall model validation. The procedure is demonstrated with a molecular replacement structure and with an experimentally-phased structure, and a variation on the method is demonstrated by removing model bias from a structure from the Protein Data Bank.

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As part of a study to characterize the detailed coordination behavior of Pu(IV), single crystal X-ray diffraction structures have been determined for Pu(IV) and Ce(IV) complexes with the naturally-occurring ligand maltol (3-hydroxy-2-methyl-pyran-4-one) and its derivative bromomaltol (5-bromo-3-hydroxy-2-methyl-pyran-4-one). Although Ce(IV) is generally accepted as a structural analog for Pu(IV), and the maltol complexes of these two metals are isostructural, the corresponding bromomaltol complexes are strikingly different with respect to ligand orientation about the metal ion: All complexes exhibit trigonal dodecahedral coordination geometry but the Ce(IV)-bromomaltol complex displays an uncommon ligand arrangement not mirrored in the Pu(IV) complex, although the two metal species are generally accepted to be structural analogs.

Gas hydrates are a vast energy resource with global distribution in the permafrost and in the oceans. Even if conservative estimates are considered and only a small fraction is recoverable, the sheer size of the resource is so large that it demands evaluation as a potential energy source. In this review paper, we discuss the distribution of natural gas hydrate accumulations, the status of the primary international R&D programs, and the remaining science and technological challenges facing commercialization of production. After a brief examination of gas hydrate accumulations that are well characterized and appear to be models for future development and gas production, we analyze the role of numerical simulation in the assessment of the hydrate production potential, identify the data needs for reliable predictions, evaluate the status of knowledge with regard to these needs, discuss knowledge gaps and their impact, and reach the conclusion that the numerical simulation capabilities are quite advanced and that the related gaps are either not significant or are being addressed. We review the current body of literature relevant to potential productivity from different types of gas hydrate deposits, and determine that there are consistent indications of a large production potential at high rates over …

Spatial resolution tests were performed on beamline 1.4.4 at the Advanced Light Source in Berkeley, CA, USA, a third-generation synchrotron light source. This beamline couples the high-brightness synchrotron source to a Thermo-Electron Continumum XL infrared microscope. Two types of resolution tests were performed in both the mid-IR and near-IR. The results are compared with a diffraction-limited spot size theory. At shorter near-IR wavelengths the experimental results begin to deviate from diffraction-limited so a combined diffraction-limit and electron-beam-source-size model is employed. This description shows how the physical electron beam size of the synchrotron source begins to dominate the focused spot size at higher energies. The transition from diffraction-limited to electron-beam-size-limited performance is a function of storage-ring parameters and the optical demagnification within the beamline and microscope optics. The discussion includes how different facilities, beamlines and microscopes will affect the achievable spatial resolution. As synchrotron light sources and other next-generation accelerators such as energy-recovery LINACs and free-electron lasers achieve smaller beam emittances, beta-functions and/or energy spreads, diffraction-limited performance can continue to higher-energy beams, perhaps ultimately into the extreme ultraviolet.

Though many enzymes can promote chemical reactions by tuning substrate properties purely through the electrostatic environment of a docking cavity, this strategy has proven challenging to mimic in synthetic host-guest systems. Here we report a highly-charged, water soluble, metal-ligand assembly with a hydrophobic interior cavity that thermodynamically stabilizes protonated substrates and consequently catalyzes the normally acidic hydrolysis of orthoformates in basic solution, with rate accelerations of up to 890-fold. The catalysis reaction obeys Michaelis-Menten kinetics, exhibits competitive inhibition, and the substrate scope displays size selectivity consistent with the constrained binding environment of the molecular host. Synthetic chemists have long endeavored to design host molecules capable of selectively binding slow-reacting substrates and catalyzing their chemical reactions. While synthetic catalysts are often site-specific and require certain properties of the substrate to insure catalysis, enzymes are often able to modify basic properties of the bound substrate such as pK{sub a} in order to enhance reactivity. Two common motifs used by nature to activate otherwise unreactive compounds are the precise arrangement of hydrogen-bonding networks and electrostatic interactions between the substrate and adjacent residues of the protein. Precise arrangement of hydrogen bonding networks near the active sites of proteins can lead to well-tuned pK{sub a}-matching, …

Sayers and Kachanov (1991) defined crack-influence parameters that are shown to be directly related to Thomsen (1986) weak-anisotropy seismic parameters for fractured reservoirs when the crack/fracture density is small enough. These results are then applied to the problem of seismic wave propagation in polar (i.e., non-isotropic) reservoirs having HTI seismic wave symmetry due to the presence of aligned vertical fractures and resulting in azimuthal seismic wave symmetry at the earth's surface. The approach presented suggests one method of inverting for fracture density from wave-speed data. It is also observed that the angular location {theta}{sub ex} of the extreme value (peak or trough) of the quasi-SV-wave speed for VTI occurs at an angle determined approximately by the formula tan{sup 2} {theta}{sub ex} {approx_equal} tan {theta}{sub m} = [(c{sub 33} - c{sub 44})/(c{sub 11}-c{sub 44})]{sup 1/2}, where {theta}{sub m} is an angle determined directly (as shown) from the c{sub ij} elastic stiffnesses, whenever these are known from either quasi-static or seismic wave measurements. Alternatively, {theta}{sub ex} is given in terms of the Thomsen seismic anisotropy parameters by tan {theta}{sub ex} {approx_equal} ([v{sub p}{sup 2}(0)-v{sub s}{sup 2}(0)]/[(1 + 2{epsilon})v{sub p}{sup 2}(0)-v{sub s}{sup 2}(0)]){sup 1/4}, where {epsilon} = (c{sub 11}-c{sub 33})/2c{sub 33}, v{sub p}{sup …

The data model for event reconstruction (EDM) in the Inner Detector of the ATLAS experiment is presented. Different data classes represent evolving stages in the reconstruction data flow, and specific derived classes exist for the sub-detectors. The Inner Detector EDM also extends the data model for common tracking in ATLAS and is integrated into the modular design of the ATLAS high-level trigger and off-line software.

{sup 137}Cs released during 1954-1974 from nuclear production reactors on the Savannah River Site, a US Department of Energy nuclear materials production site in South Carolina, contaminated a portion of the Savannah River floodplain known as Creek Plantation. {sup 137}Cs activity concentrations have been measured in Creek Plantation since 1974 making it possible to calculate effective half-lives for {sup 137}Cs in soil and vegetation and assess the spatial distribution of contaminants on the floodplain. Activity concentrations in soil and vegetation were higher near the center of the floodplain than near the edges as a result of frequent inundation coupled with the presence of low areas that trapped contaminated sediments. {sup 137}Cs activity was highest near the soil surface, but depth related differences diminished with time as a likely result of downward diffusion or leaching. Activity concentrations in vegetation were significantly related to concentrations in soil. The plant to soil concentration ratio (dry weight) averaged 0.49 and exhibited a slight but significant tendency to decrease with time. The effective half-lives for {sup 137}Cs in shallow (0-7.6 cm) soil and in vegetation were 14.9 (95% CI = 12.5-17.3) years and 11.6 (95% CI = 9.1-14.1) years, respectively, and rates of {sup 137}Cs …