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Alpine glaciers are valuable archives for the reconstruction of human impact on the environment. Besides dating purposes, measurement of radiocarbon (14C) content provides a powerful tool for long-term source apportionment studies on the carbonaceous aerosols incorporated in ice cores. In this work, we present an extraction system for 14C analyses of dissolved organic carbon (DOC) in ice cores. The setup can process ice samples of up to 350 g mass and offers ultra-clean working conditions for all extraction steps. A photo-oxidation method is applied by means of external UV irradiation of the sample. For an irradiation time of 30 min with catalyzation by addition of Fe2+ and H2O2, we achieve an efficiency of 96 ± 6% on average. Inert gas working conditions and stringent decontamination procedures enable a low overall blank of 1.9 ± 1.6 μg C with a F14C value of 0.68 ± 0.13. This makes it possible to analyze the DOC in ice samples with a carbon content of as low as 25 μg C kg−1 ice. For a first validation, the new method was applied to ice core samples from the Swiss Alps. The average DOC concentration and F14C values for the Fiescherhorn ice core samples show good agreement with previously reported data for the investigated period of 1925–1936 AD.
A recently developed dating method for glacier ice, based on the analysis of radiocarbon in carbonaceous aerosol particles, is thoroughly investigated. We discuss the potential of this method to achieve a reliable dating using examples from a mid- and a low-latitude ice core. Two series of samples from Colle Gnifetti (4450 m a.s.l., Swiss Alps) and Nevado Illimani (6300 m a.s.l., Bolivian Andes) demonstrate that the 14C ages deduced from the water-insoluble organic carbon fraction represent the age of the ice. Sample sizes ranged between 7 and 100 μg carbon. For validation we compare our results with those from independent dating. This new method is thought to have major implications for dating non-polar ice cores in the future, as it provides complementary age information for time periods not accessible with common dating techniques.
The δ-FeZn10 phase possesses high structural complexity typical of complex metallic alloys: a giant unit cell comprising 556 atoms, polyhedral atomic order with icosahedrally-coordinated environments, fractionally occupied lattice sites and statistically disordered atomic clusters that introduce intrinsic disorder into the structure. The electrical resistivity is large and exhibits a maximum at about 220 K. The magnetoresistance is sizeable, amounting to 1.5 % at 2 K in 9 T field. The temperature–dependent resistivity is discussed within the frame of the theory of slow charge carriers, applicable to metallic systems with weak dispersion of the electronic bands, where the electron motion changes from ballistic to diffusive upon heating. A comparison to the theory of weak localization is also made.
Recent exploratory syntheses of polar intermetallic compounds containing gold have established gold’s tremendous ability to stabilize new phases with diverse and fascinating structural motifs. In particular, Au-rich polar intermetallics contain Au atoms condensed into tetrahedra and diamond-like three-dimensional frameworks. In Au-poor intermetallics, on the other hand, Au atoms tend to segregate, which maximizes the number of Au-heteroatom contacts. Lastly, among polar intermetallics with intermediate Au content, complex networks of icosahedra have emerged, including discovery of the first sodium-containing, Bergman-type, icosahedral quasicrystal. Gold’s behavior in this metal-rich chemistry arises from its various atomic properties, which influence the chemical bonding features of gold with its environment in intermetallic compounds. Thus, the structural versatility of gold and the accessibility of various Au fragments within intermetallics are opening new insights toward elucidating relationships among metal-rich clusters and bulk solids.
Based on X-ray photoelectron spectroscopy, Gd5Ge4(010) does not show evidence of surface segregation. Scanning tunneling microscopy reveals two types of terraces which alternate laterally on the surface. From the step heights, these two surface terminations are assigned as dense, Gd-pure layers in the bulk structure. There is evidence of reconstruction on one type of terrace.
We have used thermal desorption spectroscopy to carry out a comparative study of potassium adsorption on Al(111) and on the fivefold Al-Pd-Mn surface. Potassium adsorption on the quasicrystal was found to be different than on Al(111). The potassium monolayer desorbed from fivefold Al-Pd-Mn at lower temperatures than from Al(111). Potassium is known to form a dense monolayer on Al(111), with an ideal coverage of 0.33, but for the monolayer on fivefold Al Pd Mn we find that the saturation coverage is only one twelfth.
An experimental comparison has been made between the properties of the surfaces of an Al70Pd21Mn9 quasicrystal and its Al48Pd42Mn10 approximant. The Al70Pd21Mn9 sample was a single grain icosahedral quasicrystal cut to expose its five-fold symmetric (000001) surface. The approximant was polycrystalline β-phase Al48Pd42Mn10, which has a CsCl-type cubic structure. Surfaces of both were prepared under ultra-high vacuum (UHV) conditions and then used for comparative measurements of their frictional properties and oxidation rates. Both materials are oxidized by reaction with O2 to form a thin film of aluminum oxide that ultimately passivates their surfaces. The interesting difference between the two is that the rate of oxidation of the approximant is significantly higher than that of the quasicrystal in spite of the fact that the bulk Al concentration of the approximant is lower than that of the quasicrystal. Friction measurements were made under UHV conditions between pairs of quasicrystals and pairs of approximants whose surfaces were either clean or oxidized to varying degrees. The friction between pairs of the approximant surfaces is significantly higher than that measured between the quasicrystal surfaces under all conditions of surface oxidation.
The ten-fold surface of the decagonal Al72Ni11Co17 (d-Al-Ni-Co) quasicrystal has been investigated using low energy electron diffraction (LEED), spot profile analysis LEED (SPA- LEED), Auger electron spectroscopy (AES) and scanning tunnelling microscopy (STM). This was done as a function of both annealing temperature and annealing time. The long-range order of the surface, as indicated by LEED, increases both as a function of annealing time and temperature. STM shows the surface to be rough and cluster-like at low annealing temperatures (≤725 K), whilst annealing to temperatures in excess of 725 K results in the formation of terraces. These terraces are small (≤ 100 Å width) at lower annealing temperatures and increase in size (100 Å ≤ x ≤ 500 Å) as the annealing temperature is increased (≥ 850 K). They are characterised by the presence of three-fold protrusions which align preferentially. STM images show single height steps as expected due to the periodicity of d-Al-Ni-Co in the z direction. To date it has not been possible to obtain atomic resolution, although this work is continuing.
Energy-angle distributions of low-energy inert-gas ions scattered from surfaces provide information about surface composition and structure. We have measured energy spectra of He+ scattered from an Al71Pd20Mn9 quasicrystal, which was oriented perpendicular to the 5-fold axis, along various azimuthal directions. Strong scattering signals are seen from Al and Pd, but only a weak Mn signal is observed. From measurements made of He+ at an oblique angle of incidence scattered in the forward direction, we observe a 72° periodicity in the azimuthal dependence of the scattering signal intensity from Al surface atoms. The effect arises from shadowing effects involving neighboring surface atoms and provides direct evidence that Al surface atoms exist in a local environment with 5-fold symmetry. In addition, measuring the variation of the signal intensity with incidence angle provides information about neighboring atom distances, which compare favorably with a model of the quasicrystal surface derived from the bulk structure.
An Al-Pd-Mn cubic alloy having a bulk chemical composition somewhat analogous to that of the icosahedral Al-Pd-Mn quasicrystal is studied. Our goal is to compare the surface structure and properties of the cubic alloy with those of the quasicrystalline alloy. In this paper, we report the first observations for the (110) surface of the cubic alloy using (primarily) low energy electron diffraction (LEED). The surface is prepared by sputtering and annealing in ultrahigh vacuum (UHV). In addition to the substrate LEED pattern, at least three superstructures evolve sequentially with annealing temperature.
Over the last few years, work in our laboratories in Ames has focussed on elucidating the surface characteristics of Al-based quasicrystalline materials, namely icosahedral (i-) Al-Cu-Fe and i-Al-Pd-Mn. Our work involves the study of the clean surfaces of these materials under ultrahigh vacuum conditions. We find that surfaces cleaned by Ar+ sputtering are depleted in Al relative to the bulk composition. Single grains, after sputtering, undergo a two-stage regrowth process as they are annealed. After heating to about 600 K, a crystalline overlayer is formed. This is rather abruptly replaced at about 750 K by a surface that appears quasicrystalline within the resolution of the experimental techniques used. Calculations based on low-energy electron diffraction (LEED) measurements of this higher temperature state indicate that the Al-rich layers in the bulk model of these materials are the favored surface terminations. Results of low-energy ion scattering (LEIS) corroborate this finding. Consistent with this, we find that the oxidation behavior and general reactivity of these materials are analogous to pure Al.
We show that friction anisotropy is an intrinsic property of the atomic structure of Al–Ni–Co decagonal quasicrystals and not only of clean and well-ordered surfaces that can be prepared in vacuum [J.Y. Park et al., Science309, 1354 (2005)]. Friction anisotropy is manifested in both nanometer-size contacts obtained with sharp atomic force microscope tips and macroscopic contacts produced in pin-on-disk tribometers. We show that the friction anisotropy, which is not observed when an amorphous oxide film covers the surface, is recovered when the film is removed due to wear. Equally important is the loss of the friction anisotropy when the quasicrystalline order is destroyed due to cumulative wear. These results reveal the intimate connection between the mechanical properties of these materials and their peculiar atomic structure.
While oral polio vaccine (OPV) has been shown to be safe and effective, it has been observed that it can circulate within a susceptible population and revert to a virulent form. Inactivated polio vaccine (IPV) confers protection from paralytic disease, but provides limited protection against infection. It is possible, then, that an IPV-immunized population, when exposed to OPV, could sustain undetected circulation of vaccine-derived poliovirus. This study examines the possibility of polio vaccine virus circulating within the United States (highly IPV-immunized) population that borders Mexico (OPV-immunized). A total of 653 stool and 20 sewage samples collected on the US side of the border were tested for the presence of poliovirus. All samples were found to be negative. These results suggest that the risk of circulating vaccine-derived poliovirus is low in fully immunized IPV-using populations in developed countries that border OPV-using populations.
The potential for future commercialization of glyphosate-resistant wheat necessitates evaluation of agronomic merits of this technology. Experiments were established to evaluate glyphosate-resistant wheat and weed responses to glyphosate rate, application timing, and tank mixtures. Glyphosate at 1,680 g/ha did not injure wheat. Wheat response to glyphosate applied to one- to three- or three- to five-leaf wheat was not different from that of untreated wheat. Wheat was injured more from glyphosate plus thifensulfuron or glyphosate plus dicamba than from individual herbicides at one of six locations, but grain yield was not affected by glyphosate tank mixtures. Glyphosate application timing did not affect control of wild oat or common lambsquarters 56 d after treatment. Glyphosate when applied to one- to three-leaf wheat provided better control of wild buckwheat than later glyphosate application, whereas glyphosate applied to three- to five-leaf wheat provided the best control of green and yellow foxtail, redroot pigweed, and Canada thistle. Weed control with glyphosate tended to be better than with conventional herbicides, and wheat treated with glyphosate produced approximately 10% more grain than wheat treated with conventional herbicide tank mixes.
The tribological properties of a B2-type Al–Pd–Mn quasicrystal approximant were investigated and compared with those of an Al–Pd–Mn icosahedral quasicrystal. The approximant was of the _ phase, having a crystalline CsCl-type structure and nominal composition Al48Pd42Mn10. Friction coefficients measured in ultrahigh vacuum between a pair of Al48Pd42Mn10 samples having truly clean surfaces were found to be twice as high as those reported for the Al70Pd21Mn9 quasicrystal. When the surfaces were oxidized by exposure to O2 or H2O, the friction coefficients decreased by roughly a factor of two for both materials but the friction coefficient for the approximant remained roughly twice that of the quasicrystal. The rate of oxidation of the approximant was found to be one order of magnitude higher than that of the quasicrystal. This corroborates findings that suggest that quasicrystals exhibit an inherent resistance to oxidation and corrosion. Vickers hardness measurements show that the quasicrystal is roughly three times as hard as the approximant.
A variety of opportunities to develop technological applications of quasicrystals is being considered. Several of these are discussed in this issue. A common feature of many proposed applications is that they involve surface or near-surface interactions. Information about the surface structure, composition, and chemistry is prerequisite to understanding the origin of the desirable traits of quasicrystals. For instance, basic issues of surface structure—whether quasicrystals are intrinsically rough or flat, quasicrystalline or not quasicrystalline—impact directly on our understanding of their surface thermodynamic, electronic, and chemical properties.
Results are presented of five consecutive annual examinations using the Abnormal Involuntary Movement Scale for 101 community-based chronic psychiatric patients. These 101 patients had a history of longer and more consistent neuroleptic treatment than the 231 patients who initially entered the study, so no conclusions about prevalence of TD can be drawn. At each examination two-thirds of this group showed signs of TD; however, only 45% were TD positive at most examinations and 24% were best described as having fluctuating TD status. Of those patients who were consistently TD positive, 82% showed no overall significant change in summed AIMS scores, 11% improved and 7% became worse.