Crystallization conditions and controls on trace element residence in the main minerals from the Pedra Branca Syenite, Brazil: An electron microprobe and LA-ICPMS study

Major and trace-element microanalyses of the main minerals from the 610 Ma Pedra Branca Syenite, southeast Brazil, allow inferences on intensive parameters of magmatic crystallization and on the partition of trace-elements among these minerals, with important implications for the petrogenetic evolution of the pluton. Two main syenite types make up the pluton, a quartz-free syenite with tabular alkali feldspar (laminated silica-saturated syenite, LSS, with Na-rich augite + phlogopite + hematite + magnetite + titanite + apatite) and a quartz-bearing syenite (laminated silica-oversaturated syenite, LSO, with scarce corroded plagioclase plus diopside + biotite +/- hornblende + ilmenite magnetite +/- titanite + apatite). Both types share a remarkable enrichment in incompatible elements as K, Ba, Sr, P and LREE. Apatite saturation temperatures of similar to 1060-1090 degrees C are the best estimates of liquidus, whereas the pressure of emplacement, based on Al-in-hornblende barometry, is estimated as 3.3 to 4.8 khan Although both units crystallized under oxidizing conditions, oxygen fugacity was probably higher in LSS, as shown by higher mg# of the mafic minerals and higher hematite contents in Hem-Ilm(ss). In contrast with the Ca-bearing alkali-feldspar from LSO, which hosts most of the whole-rock Sr and Pb, virtually Ca-free alkali-feldspar from LSS hosts similar to 50% of whole-rock Sr and similar to 80% of Pb, the remainder of these elements being shared by apatite, pyroxene and titanite. This contrast reflects a strong crystal-chemical control, whereby a higher proportion of an element with similar ratio and charge (Ca2+) enhances the residence of Sr and Pb in the M-site of alkali feldspar. The more alkaline character of the LSS magma is inferred to have inhibited zircon saturation; Zr + Hf remained in solution until late in the crystallization, and were mostly accommodated in the structure of Ca-Na pyroxene and titanite, which are one order of magnitude richer in these elements compared to the same minerals in LSO, where most of Zr and Hf are inferred to reside in zircon. The REE, Th and U reside mostly in titanite and apatite; D(REE)Tit/Ap raises steadily from 1 to 6 from La to Tb then remains constant up to Lu in the LSO sample; these values are about half as much in the LSS sample, where lower contents of incompatible elements in titanite are attributed to its greater modal abundance and earlier crystallization. (C) 2012 Elsevier B.V. All rights reserved.

Origin of Anomalous Activities for Electrocatalysts in Alkaline Electrolytes

Pt extended surfaces and nanoparticle electrodes are used to understand the origin of anomalous activities for electrocatalytic reactions in alkaline electrolytes as a function of cycling/time. Scanning tunneling microscopy (STM) of the surfaces before and after cycling in alkaline electrolytes was used to understand the morphology of the impurities and their impact on the catalytic sites. The nature of the contaminant species is identified as 3d-transition metal cations, and the formation of hydr(oxy)oxides of these elements is established as the main reason for the observed behavior. We find that, while for the oxygen reduction reaction (ORR) and the hydrogen oxidation reaction (HOR) the blocking of the sites by the undesired 3d-transition metal hydr(oxy)oxide species leads to deactivation of the reaction activities, the CO oxidation reaction and the hydrogen evolution reaction (HER) can have beneficial effects from the same impurities, the latter being dependent on the exact nature of the adsorbing species. These results show the significance of impurities present in real electrolytes and their impact on electrocatalysis.

Rock Art at the Pleistocene/Holocene Boundary in Eastern South America

Background: Most investigations regarding the First Americans have primarily focused on four themes: when the New World was settled by humans; where they came from; how many migrations or colonization pulses from elsewhere were involved in the process; and what kinds of subsistence patterns and material culture they developed during the first millennia of colonization. Little is known, however, about the symbolic world of the first humans who settled the New World, because artistic manifestations either as rock-art, ornaments, and portable art objects dated to the Pleistocene/Holocene transition are exceedingly rare in the Americas. Methodology/Principal Findings: Here we report a pecked anthropomorphic figure engraved in the bedrock of Lapa do Santo, an archaeological site located in Central Brazil. The horizontal projection of the radiocarbon ages obtained at the north profile suggests a minimum age of 9,370640 BP, (cal BP 10,700 to 10,500) for the petroglyph that is further supported by optically stimulated luminescence (OSL) dates from sediment in the same stratigraphic unit, located between two ages from 11.7 +/- 0.8 ka BP to 9.9 +/- 0.7 ka BP. Conclusions: These data allow us to suggest that the anthropomorphic figure is the oldest reliably dated figurative petroglyph ever found in the New World, indicating that cultural variability during the Pleistocene/Holocene boundary in South America was not restricted to stone tools and subsistence, but also encompassed the symbolic dimension.

Alkaline sulfite/anthraquinone pretreatment followed by disk refining of Pinus radiata and Pinus caribaea wood chips for biochemical ethanol production

BACKGROUND: Alkaline sulfite/anthraquinone (ASA) cooking of Pinus radiata and Pinus caribaea wood chips followed by disk refining was used as a pretreatment for the production of low lignified and high fibrillated pulps. The pulps produced with different delignification degrees and refined at different energy inputs (250, 750 and 1600 Wh) were saccharified with cellulases and fermented to ethanol with Saccharomyces cerevisiae using separated hydrolysis and fermentation (SHF) or semi-simultaneous saccharification and fermentation (SSSF) processes. RESULTS: Delignification of ASA pulps was between 25% and 50%, with low glucans losses. Pulp yield was from 70 to 78% for pulps of P. radiata and 60% for the pulp of P. caribaea. Pulps obtained after refining were evaluated in assays of enzymatic hydrolysis. Glucans-to-glucose conversion varied from 20 to 70%, depending on the degree of delignification and fibrillation of the pulps. The best ASA pulp of P. radiata was used in SHF and SSSF experiments of ethanol production. Such experiments produced maximum ethanol concentration of 20 g L-1, which represented roughly90% of glucose conversion and an estimated amount of 260 L ethanol ton(-1) wood. P. caribaea pulp also presented good performance in the enzymatic hydrolysis and fermentation but, due to the low amount of cellulose present, only 140 L ethanol would be obtained from each ton of wood. CONCLUSION: ASA cooking followed by disk refining was shown to be an efficient pretreatment process, which generated a low lignified and high-fibrillated substrate that allowed the production of ethanol from the softwoods with high conversion yields. (C) 2012 Society of Chemical Industry

Mass balance of pilot-scale pretreatment of sugarcane bagasse by steam explosion followed by alkaline delignification

Five pilot-scale steam explosion pretreatments of sugarcane bagasse followed by alkaline delignification were explored. The solubilised lignin was precipitated with 98% sulphuric acid. Most of the pentosan (82.6%), and the acetyl group fractions were solubilised during pretreatment, while 90.2% of cellulose and 87.0% lignin were recovered in the solid fraction. Approximately 91% of the lignin and 72.5% of the pentosans contained in the steam-exploded solids were solubilised by delignification, resulting in a pulp with almost 90% of cellulose. The acidification of the black liquors allowed recovery of 48.3% of the lignin contained in the raw material. Around 14% of lignin, 22% of cellulose and 26% of pentosans were lost during the process. In order to increase material recovery, major changes, such as introduction of efficient condensers and the reduction in the number of washing steps, should be done in the process setup. (C) 2012 Elsevier Ltd. All rights reserved.

Investigation of the Goias Alkaline Province, Central Brazil: Application of gravity and magnetic methods

We investigate the strong magnetic and gravity anomalies of the Goias Alkaline Province (GAP), a region of Late Cretaceous alkaline magmatism along the northern border of the Parana Basin, Brazil. The alkaline complexes (eight of which are present in outcrops, two others inferred from magnetic signals) are characterized by a series of small intrusions forming almost circular magnetic and gravimetric anomalies varying from -4000 to +6000 nT and from -10 to +40 mGal, respectively. We used the Aneuler method and Analytical Signal Amplitude to obtain depth and geometry for mapped sources from the magnetic anomaly data. These results were used as the reference models in the 3D gravity inversion. The 3D inversion results show that the alkaline intrusions have depths of 10-12 km. The intrusions in the northern GAP follow two alignments and have different sizes. In the anomaly magnetic map, dominant guidelines correlate strongly with the extensional regimes that correlate with the rise of alkaline magmatism. The emplacement of these intrusions marks mechanical discontinuities and zones of weakness in the upper crust. According to the 3D inversion results, those intrusions are located within the upper crust (from the surface to 18 km depth) and have spheres as the preferable geometry. Such spherical shapes are more consistent with magmatic chambers instead of plug intrusions. The Registro do Araguaia anomaly (similar to 15 by 25 km) has a particular magnetic signature that indicates that the top is deeper than 1500 m. North of this circular anomaly are lineaments with structural indices indicating contacts on their edges and dikes/sills in the interiors. Results of 3D inversion of magnetic and gravity data suggest that the Registro do Araguaia is the largest body in the area, reaching 18 km depth and indicating a circular layered structure. (C) 2011 Elsevier Ltd. All rights reserved.

Audiological and electrophysiological assessment of professional pop/rock musicians

In the present study, we evaluated peripheral and central auditory pathways in professional musicians (with and without hearing loss) compared to non-musicians. The goal was to verify if music exposure could affect auditory pathways as a whole. This is a prospective study that compared the results obtained between three groups (musicians with and without hearing loss and non-musicians). Thirty-two male individuals participated and they were assessed by: Immittance measurements, pure-tone air conduction thresholds at all frequencies from 0.25 to 20 kHz, Transient Evoked Otoacoustic Emissions, Auditory Brainstem Response (ABR), and Cognitive Potential. The musicians showed worse hearing thresholds in both conventional and high frequency audiometry when compared to the non-musicians; the mean amplitude of Transient Evoked Otoacoustic Emissions was smaller in the musicians group, but the mean latencies of Auditory Brainstem Response and Cognitive Potential were diminished in the musicians when compared to the non-musicians. Our findings suggest that the population of musicians is at risk for developing music-induced hearing loss. However, the electrophysiological evaluation showed that latency waves of ABR and P300 were diminished in musicians, which may suggest that the auditory training to which these musicians are exposed acts as a facilitator of the acoustic signal transmission to the cortex.

Evaluation of Chemical Treatment on Zirconia Surface with Two Primer Agents and an Alkaline Solution on Bond Strength

Objectives: This study evaluated the effect of an alkaline solution and two 10-methacryloyloxydecyl dihydrogen phosphate (MDP)-based primer agents on bond strength to zirconia (yttria-stabilized tetragonal zirconium polycrystal [Y-TZP]) through the shear bond strength (SBS) test. Materials and Methods: Sixty square-shaped Y-TZP samples were embedded in an acrylic resin mold, polished, and randomly assigned to one of six groups (n=10) according to treatment surface: group CR, no treatment (control); group NaOH, 0.5 M NaOH; group AP, Alloy Primer; group ZP, Z-Primer Plus; group NaOH-AP, 0.5 M NaOH + Alloy Primer; and group NaOH-ZP, 0.5 M NaOH + Z-Primer Plus. The resin cement (Rely X U100) was applied inside a matrix directly onto the Y-TZP surface, and it was light-cured for 40 seconds. The samples were stored in distilled water at 37 C for 24 hours prior to the test, which was performed in a universal machine at a crosshead-speed of 0.5 mm/min. The data were analyzed by one-way analysis of variance and Tukey tests (p<0.05). Light stereomicroscopy and scanning electron microscopy were used to assess the surface topography and failure mode. Results: The SBS was significantly affected by the chemical treatment (p<0.0001). The AP group displayed the best results, and the use of NaOH did not improve SBS results relative to either AP or ZP. The samples treated with Alloy Primer displayed mainly mixed failures, whereas those conditioned with Z-Primer Plus or with 0.5 M NaOH presented a balanced distribution of adhesive and mixed failure modes. Conclusions: The use of a NaOH solution may have modified the reactivity of the Y-TZP surface, whereas the employment of a MDP/6-4-vinylbenzyl-n-propyl amino-1,3,5-triazine2,4-dithione-based primer enhanced the Y-TZP bond strength.

Calculations of the spectral shifts and line profiles of alkaline earth atoms in liquid helium environment

Liquid configurations generated by Metropolis Monte Carlo simulations are used in time-dependent density functional theory calculations of the spectral line shifts and line profiles of the lowest lying excitation of the alkaline earth atoms, Be, Mg, Ca, Sr and Ba embedded in liquid helium. The results are in very good agreement with the available experimental data. Special attention is given to the calculated spectroscopic shift and the associated line broadening. The analysis specifies the inhomogeneous broadening of the three separate contributions due to the splitting of the s -> p transition of the alkaline earth atom in the liquid environment. (C) 2012 Elsevier B. V. All rights reserved.

Glycerol oxidation on nickel based nanocatalysts in alkaline medium – Identification of the reaction products

In this work, carbon supported nickel based nanoparticles were prepared by impregnation method and used as anode electrocatalysts for the glycerol conversion. These metallic powders were mixed with a suitable amount of a Nafion/water solution to make catalytic inks which were then deposited onto the surface of carbon Toray used as a conductive substrate. Long-term electrolyses of glycerol were carried out in alkaline medium by chronoamperometry experiments. Analysis of the oxidation products was performed with ion-exclusion liquid chromatography which separates the analytes by ascending pKa. The spectroscopic measurements have shown that the cobalt content in the anode composition did contribute to the CAC bond cleavage of the initial molecule of glycerol.

The role of asymmetries in rock-paper-scissors biodiversity models.

The maintenance of biodiversity is a long standing puzzle in ecology. It is a classical result that if the interactions of the species in an ecosystem are chosen in a random way, then complex ecosystems can't sustain themselves, meaning that the structure of the interactions between the species must be a central component on the preservation of biodiversity and on the stability of ecosystems. The rock-paper-scissors model is one of the paradigmatic models that study how biodiversity is maintained. In this model 3 species dominate each other in a cyclic way (mimicking a trophic cycle), that is, rock dominates scissors, that dominates paper, that dominates rock. In the original version of this model, this dominance obeys a 'Z IND 3' symmetry, in the sense that the strength of dominance is always the same. In this work, we break this symmetry, studying the effects of the addition of an asymmetry parameter. In the usual model, in a two dimensional lattice, the species distribute themselves according to spiral patterns, that can be explained by the complex Landau-Guinzburg equation. With the addition of asymmetry, new spatial patterns appear during the transient and the system either ends in a state with spirals, similar to the ones of the original model, or in a state where unstable spatial patterns dominate or in a state where only one species survives (and biodiversity is lost).