A quasiclassical trajectory study of the OH plus SO reaction: The role of rotational energy

A full dimensional quasiclassical trajectory study of the OH+SO reaction is presented with the aim of investigating the role of the reactants rotational energy in the reactivity. Different energetic combinations with one and both reactants rotationally excited are studied. A passive method is used to correct zero-point-energy leakage in the classical calculations. The reactive cross sections, for each combination, are calculated and fitted to a capturelike model combined with a factor accounting for recrossing effects. Reactivity decreases as rotational energy is increased in any of both reactants. This fact provides a theoretical support for the experimental dependence of the rate constant on temperature.

Magnons in a Ferromagnetic Monolayer

We report the first observation of high wave vector magnon excitations in a ferromagnetic monolayer. Using spin-polarized electron energy loss spectroscopy, we observed the magnon dispersion in one atomic layer (ML) of Fe on W(110) at 120 K. The magnon energies are small in comparison to the bulk and surface Fe(110) excitations. We find an exchange parameter and magnetic anisotropy similar to that from static measurements. Our results are in sharp contrast to theoretical calculations, indicating that the present understanding of magnetism of the ML Fe requires considerable revision.

Awaking the Vacuum in Relativistic Stars

Void of any inherent structure in classical physics, the vacuum has revealed to be incredibly crowded with all sorts of processes in relativistic quantum physics. Yet, its direct effects are usually so subtle that its structure remains almost as evasive as in classical physics. Here, in contrast, we report on the discovery of a novel effect according to which the vacuum is compelled to play an unexpected central role in an astrophysical context. We show that the formation of relativistic stars may lead the vacuum energy density of a quantum field to an exponential growth. The vacuum-driven evolution which would then follow may lead to unexpected implications for astrophysics, while the observation of stable neutron-star configurations may teach us much on the field content of our Universe.

Strong reduction of V(4+) amount in vanadium oxide/hexadecylamine nanotubes by doping with Co(2+) and Ni(2+) ions: Electron paramagnetic resonance and magnetic studies

In this work we present a complete characterization and magnetic study of vanadium oxide/hexadecylamine nanotubes (VO(x)/Hexa NT's) doped with Co(2)+ and Ni(2+) ions. The morphology of the NT's has been characterized by transmission electron microscopy, while the metallic elements have been quantified by the instrumental neutron activation analysis technique. The static and dynamic magnetic properties were studied by collecting data of magnetization as a function of magnetic field and temperature and by electron paramagnetic resonance. At difference of the majority reports in the literature, we do not observe magnetic dimers in vanadium oxide nanotubes. Also, we observed that the incorporation of metallic ions (Co(2+), S = 3/2 and Ni(2+), S = 1) decreases notably the amount of V(4+) ions in the system, from 14-16% (nondoped case) to 2%-4%, with respect to the total vanadium atoms (fact corroborated by XPS experiments) anyway preserving the tubular nanostructure. The method to decrease the amount of V(4+) in the nanotubes improves considerably their potential technological applications as Li-ion batteries cathodes. (C) 2011 American Institute of Physics. [doi: 10.1063/1.3580252]

Intermolecular vibrations and fast relaxations in supercooled ionic liquids

Short-time dynamics of ionic liquids has been investigated by low-frequency Raman spectroscopy (4 < omega < 100 cm(-1)) within the supercooled liquid range. Raman spectra are reported for ionic liquids with the same anion, bis(trifluoromethylsulfonyl)imide, and different cations: 1-butyl-3-methylimidazolium, 1-hexyl-3-methylimidazolium, 1-butyl-1-methylpiperidinium, trimethylbutylammonium, and tributylmethylammonium. It is shown that low-frequency Raman spectroscopy provides similar results as optical Kerr effect (OKE) spectroscopy, which has been used to study intermolecular vibrations in ionic liquids. The comparison of ionic liquids containing aromatic and non-aromatic cations identifies the characteristic feature in Raman spectra usually assigned to librational motion of the imidazolium ring. The strength of the fast relaxations (quasi-elastic scattering, QES) and the intermolecular vibrational contribution (boson peak) of ionic liquids with non-aromatic cations are significantly lower than imidazolium ionic liquids. A correlation length assigned to the boson peak vibrations was estimated from the frequency of the maximum of the boson peak and experimental data of sound velocity. The correlation length related to the boson peak (similar to 19 angstrom) does not change with the length of the alkyl chain in imidazolium cations, in contrast to the position of the first-sharp diffraction peak observed in neutron and X-ray scattering measurements of ionic liquids. The rate of change of the QES intensity in the supercooled liquid range is compared with data of excess entropy, free volume, and mean-squared displacement recently reported for ionic liquids. The temperature dependence of the QES intensity in ionic liquids illustrates relationships between short-time dynamics and long-time structural relaxation that have been proposed for glass-forming liquids. (C) 2011 American Institute of Physics. [doi: 10.1063/1.3604533]

k(0)-INAA for determining chemical elements in bird feathers

The k(0)-method instrumental neutron activation analysis (k(0)-INAA) was employed for determining chemical elements in bird feathers. A collection was obtained taking into account several bird species from wet ecosystems in diverse regions of Brazil. For comparison reason, feathers were actively sampled in a riparian forest from the Marins Stream, Piracicaba, Sao Paulo State, using mist nets specific for capturing birds. Biological certified reference materials were used for assessing the quality of analytical procedure. Quantification of chemical elements was performed using the k(0)-INAA Quantu Software. Sixteen chemical elements, including macro and micronutrients, and trace elements, have been quantified in feathers, in which analytical uncertainties varied from 2% to 40% depending on the chemical element mass fraction. Results indicated high mass fractions of Br (max=7.9 mgkg(-1)), Co (max= 0.47 mg kg(-1)), Cr (max =68 mg kg(-1)), Hg (max =2.79 mg kg(-1)), Sb (max= 0.20 mg kg(-1)), Se (max=1.3 mg kg(-1)) and Zn (max =192 mg kg(-1)) in bird feathers, probably associated with the degree of pollution of the areas evaluated. In order to corroborate the use of k(0)-INAA results in biomonitoring studies using avian community, different factor analysis methods were used to check chemical element source apportionment and locality clustering based on feather chemical composition. (C) 2010 Elsevier B.V. All rights reserved.

Characterizing suspended sediments from the Piracicaba River Basin by means of k(0)-INAA

The inorganic chemical characterization of suspended sediments is of utmost relevance for the knowledge of the dynamics and movement of chemical elements in the aquatic and wet ecosystems. Despite the complexity of the effective design for studying this ecological compartment, this work has tested a procedure for analyzing suspended sediments by instrumental neutron activation analysis, k(0) method (k(0)-INAA). The chemical elements As, Ba, Br, Ca, Ce, Co, Cr, Cs, Eu, Fe, Hf, Fig, K, La, Mo, Na, Ni, Rb, Sb, Sc, Se, Sm, Sr, Ta, Tb, Th, Yb and Zn were quantified in the suspended sediment compartment by means of k(0)-INAA. When compared with World Average for rivers, high mass fractions of Fe (222,900 mg/kg), Ba (4990 mg/kg), Zn (1350 mg/kg), Cr (646 mg/kg), Co (74.5 mg/kg), Br (113 mg/kg) and Mo (31.9 mg/kg) were quantified in suspended sediments from the Piracicaba River, the Piracicamirim Stream and the Marins Stream. Results of the principal component analysis for standardized chemical element mass fractions indicated an intricate correlation among chemical elements evaluated, as a response of the contribution of natural and anthropogenic sources of chemical elements for ecosystems. (C) 2010 Elsevier B.V. All rights reserved.

Fertilizers applied to certified organic tomato culture

The tomato culture demands large quantities of mineral nutrients, which are supplied by synthetic fertilizers in the conventional cultivation system. In the organic cultivation system only alternative fertilizers are allowed by the certifiers and accepted as safe for humans and environment. The chemical composition of rice bran, oyster flour, cattle manure and ground charcoal, as well as soils and tomato fruits were evaluated by instrumental neutron activation analysis (INAA). The potential contribution of organic fertilizers to the enrichment of chemical elements in soil and their transfer to fruits was investigated using concentration ratios for fertilizer and soil samples, and also for soil and tomato. Results evidenced that these alternative fertilizers could be taken as important sources of Br, Ca, Ce, K, Na and Zn for the organic tomato culture.

Improving sample representativeness in environmental studies: a major component for the uncertainty budget

For environmental quality assessment, INAA has been applied for determining chemical elements in small (200 mg) and large (200 g) samples of leaves from 200 trees. By applying the Ingamells` constant, the expected percent standard deviation was estimated in 0.9-2.2% for 200 mg samples. Otherwise, for composite samples (200 g), expected standard deviation varied from 0.5 to 10% in spite of analytical uncertainties ranging from 2 to 30%. Results thereby suggested the expression of the degree of representativeness as a source of uncertainty, contributing for increasing of the reliability of environmental studies mainly in the case of composite samples.

Collimated scanning LS-INAA for testing trace elements homogeneity in Brazilian coffee beans

The degree of homogeneity is normally assessed by the variability of the results of independent analyses of several (e.g., 15) normal-scale replicates. Large sample instrumental neutron activation analysis (LS-INAA) with a collimated Ge detector allows inspecting the degree of homogeneity of the initial batch material, using a kilogram-size sample. The test is based on the spatial distributions of induced radioactivity. Such test was applied to samples of Brazilian whole (green) coffee beans (Coffea arabica and Coffea canephora) of approximately I kg in the frame of development of a coffee reference material. Results indicated that the material do not contain significant element composition inhomogeneities between batches of approximately 30-50 g, masses typically forming the starting base of a reference material.

Status of chemical elements in Atlantic Forest tree species near an industrial complex

Environmental quality assessment studies have been conducted with tree species largely distributed in the Atlantic Forest. Leaf and soil samples were collected in the conservation unit Parque Estadual da Serra do Mar (PESM) nearby the industrial complex of Cubatao, Sao Paulo State, Brazil, and analyzed for chemical elements by instrumental neutron activation analysis. Results were compared to background values obtained in the Parque Estadual Carlos Botelho (PECB). The higher As, Fe, Hg and Zn mass fractions in the tree leaves of PESM indicated anthropogenic influence on this conservation unit.

Chemical characterization of agricultural supplies applied to organic tomato cultivation

The agricultural supplies used in the organic system to control pests and diseases as well as to fertilize soil are claimed to be beneficial to plants and innocuous to human health and to the environment. The chemical composition of six agricultural supplies commonly used in the organic tomato culture, was evaluated by instrumental neutron activation analysis (INAA). Results were compared to the maximum limits established by the Environment Control Agency of the Sao Paulo State (CETESB) and the Guidelines for Organic Quality Standard of Instituto Biodinamico (IBD). Concentrations above reference values were found for Co, Cr and Zn in compost, Cr and Zn in cattle manure and Zn in rice bran.

Elemental composition changes in citrus affected by the CVC disease

The citrus variegated chlorosis (CVC) disease results in serious economical losses for the Brazilian citriculture. The influence of CVC disease on the elemental composition of citrus plants was investigated. Leaves of sweet orange varieties Hamlin, Pera Rio and Valencia were collected from healthy and CVC-affected trees for chemical characterization by instrumental neutron activation analysis (INAA). Significant differences between healthy and CVC-affected leaves were identified for Ca, Ce, Co, Eu, Fe, K, La, Na, Nd, Rb, Sc and Sm. Rare earth elements presented consistently higher mass fractions in the healthy leaves.

Chemical composition of tomato seeds affected by conventional and organic production systems

Tomato is amongst the most consumed vegetables in the world, not only for its culinary versatility but also for its high nutritional value. In the last years, consumers have shown an increased concern regarding food origin and safety. The organic tomato production has been a promising alternative for the consumer offering a safer food in relation to environmental, social and nutritional aspects. This study assessed the chemical composition of tomato seeds produced in both conventional and organic systems by INAA. The results showed significant differences (P <= 0.05) in the mass fractions of Br, Cs, Eu, Fe, K, Mo, Na, Rb and Sm between both systems, indicating influence of the crop management adopted in the different tomato production systems.

Sampling study in milk storage tanks by INAA

This study investigated the representativeness of samples for assessing chemical elements in milk bulk tanks. Milk samples were collected from a closed tank in a dairy plant and from an open top tank in a dairy farm. Samples were analyzed for chemical elements by instrumental neutron activation analysis (INAA). For both experiments, Br, Ca, Cs, K, Na, Rb and Zn did not present significant differences between samples thereby indicating the appropriateness of the sampling procedure adopted to evaluate the analytes of interest.