Crystal growth and photoluminescence of europium-doped strontium titanate prepared by a microwave hydrothermal method

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

The influence of B4C and MgB2 additions on the behavior of MgO-C bricks

Carbon-containing refractory materials have received great attention over the last years due to their importance in the steelmaking process. The oxidation of carbon present in refractory materials at temperatures above 500 degrees C is usually accompanied by the decrease of their mechanical strength and chemical resistance. Aiming to improve the oxidation resistance of carbon-oxide refractories, the use of materials known as antioxidants has been extensively studied. In this work we evaluated the performance of MgB2 and B4C antioxidants when incorporated into MgO-C bricks. We observed that the co-addition of metallic antioxidants and B4C or MgB2 leads to refractory bricks with enhanced hot modulus of rupture and resistance against oxidation and slag corrosion. However, the excessive addition of these antioxidants could impair the performance of the obtained bricks. Thus, when determining the optimum concentration of MgB2 and B4C to be added into MgO-C refractories, one must take into consideration this behavior. (c) 2012 Elsevier Ltd and Techna Group S.r.l. All rights reserved.

Strontium zirconate heterogeneous catalyst for biodiesel production: Synthesis, characterization and catalytic activity evaluation

Strontium zirconate oxide was synthesized by co-precipitation and the citrate route and was evaluated as a heterogeneous catalyst for biodiesel production. The catalyst samples were characterized by XRD, FTIR, and TG, and catalytic activity was measured based on the ester content of the biodiesel produced that was quantified by GC. The co-precipitate samples were obtained in alkaline pH and had a mixture of the perovskite and pure strontium and zirconium oxide phases. Ester conversion using these samples was approximately 1.6%, indicating no catalytic activity. The citrate route was more efficient in producing perovskite when carried out at pH 7-8; excess SrCO3 was found on the catalyst surface due to CO2 adsorption, thus demonstrating no catalytic activity. The same synthesis carried out at pH 2 resulted in free OH- groups, with a small amount of the carbonate species that produced ester yield values of 98%. Therefore, matrices based on strontium zirconate produced via the citrate route in acidic media are potential heterogeneous catalysts for transesterification. (C) 2012 Elsevier B.V. All rights reserved.

Additions- und Umlagerungsreaktionen des Lewis-aciden Dihypersilylplumbandiyls in Umsetzungen mit monodenten und ambidenten Lewis-Basen

Die chemische Reaktivität des Dihypersilylplumbylens Pb[Si(Si(CH3)3)3]2 wird durch seine besondere elektronische Struktur bestimmt. Im Unterschied zu Carbenen (Triplett-Grundzustand) liegen Plumbylene im Grundzustand als Singulett vor, mit einem energetisch hochliegenden HOMO (freies Elektronenpaar mit hohem s-Charakter) und einem tiefliegenden LUMO (näherungsweise: freies p-Orbital des Pb-Atoms). Daraus resultiert das amphotere Lewis-Säure/Lewis-Base-Verhalten der Verbindung, mit der Besonderheit, dass sich die beiden Lewis-Zentren am selben Atom befinden. rnIn Umsetzungen mit monodenten und ambidenten Lewis-Basen wurden die Lewis-aciden Eigenschaften des Dihypersilylplumbandiyls Pb[Si(Si(CH3)3)3]2 untersucht. Reaktionen mit den sterisch anspruchsvollen O-Nucleophilen KOtBu (Kalium-tert-Butanolat) und KOiPrPh (4-Kaliumisopropylphenolat) führten bei tiefen Temperaturen zur primären Adduktbildung. Die aus der Strukturanalyse erhaltenen Bindungsdaten zeigen die extreme sterische Überfrachtung des zentralen Blei-Atoms. Der Abbau der sterischen Spannung ist möglicherweise die Ursache für offensichtlich stattfindende Umlagerungsfolgereaktionen (bei Reaktionsführungen bei T>-60°C), die aufgrund spektroskopische Untersuchungen zu vermuten sind.rnEingehender wurden diese Umlagerungsreaktionen in Umsetzungen des Pb[Si(Si(CH3)3)3]2 mit ambidenten Lewis-Basen untersucht. In Übereinstimmung und Erweiterung mit früheren Ergebnissen von Klinkhammer (K. Klinkhammer, Polyhedron, 2002, 21, 587) konnte beispielsweise die Migration einer (mit der ambidenten Lewis-Base tert-Butylisonitril) bzw. beider Hypersilylgruppen (mit p-Tolylisocyanat) unter Bildung hetero- bzw. homoleptischer Plumbylene nachgewiesen werden.rnReaktionen des Pb[Si(Si(CH3)3)3]2 mit den anorganischen ambidenten Salz-Ionen CN-, OCN-, SCN-, N3-, NO2- führen zur Bildung salzartiger Plumbanide der Zusammensetzung Me{Pb[Si(Si(CH3)3)3]2}Nu (Me: Na bzw. K, Nu: CN, OCN, SCN, N3, NO2). Die Verbindungen liegen im Kristall monomer als Kontaktionenpaar vor. Auf diese Weise gelang erstmalig die gezielte Synthese eines Blei(II)cyanids sowie die Darstellung eines Blei(II)isocyanats. rn

Geochemical and Strontium Isotope Characterization of Produced Waters from Marcellus Shale Natural Gas Extraction

Extraction of natural gas by hydraulic fracturing of the Middle Devonian Marcellus Shale, a major gas-bearing unit in the Appalachian Basin, results in significant quantities of produced water containing high total dissolved solids (TDS). We carried out a strontium (Sr) isotope investigation to determine the utility of Sr isotopes in identifying and quantifying the interaction of Marcellus Formation produced waters with other waters in the Appalachian Basin in the event of an accidental release, and to provide information about the source of the dissolved solids. Strontium isotopic ratios of Marcellus produced waters collected over a geographic range of ∼375 km from southwestern to northeastern Pennsylvania define a relatively narrow set of values (εSr SW = +13.8 to +41.6, where εSr SW is the deviation of the 87Sr/86Sr ratio from that of seawater in parts per 104); this isotopic range falls above that of Middle Devonian seawater, and is distinct from most western Pennsylvania acid mine drainage and Upper Devonian Venango Group oil and gas brines. The uniformity of the isotope ratios suggests a basin-wide source of dissolved solids with a component that is more radiogenic than seawater. Mixing models indicate that Sr isotope ratios can be used to sensitively differentiate between Marcellus Formation produced water and other potential sources of TDS into ground or surface waters.

Effects of experimental nitrogen additions on plant diversity in an old-growth tropical forest

Response of plant biodiversity to increased availability of nitrogen (N) has been investigated in temperate and boreal forests, which are typically N-limited, but little is known in tropical forests. We examined the effects of artificial N additions on plant diversity (species richness, density and cover) of the understory layer in an N saturated old-growth tropical forest in southern China to test the following hypothesis: N additions decrease plant diversity in N saturated tropical forests primarily from N-mediated changes in soil properties. Experimental additions of N were administered at the following levels from July 2003 to July 2008: no addition (Control); 50 kg N ha−1 yr−1 (Low-N); 100 kg N ha−1 yr−1 (Medium-N), and 150 kg N ha−1 yr−1 (High-N). Results showed that no understory species exhibited positive growth response to any level of N addition during the study period. Although low-to-medium levels of N addition (≤100 kg N ha−1 yr−1) generally did not alter plant diversity through time, high levels of N addition significantly reduced species diversity. This decrease was most closely related to declines within tree seedling and fern functional groups, as well as to significant increases in soil acidity and Al mobility, and decreases in Ca availability and fine-root biomass. This mechanism for loss of biodiversity provides sharp contrast to competition-based mechanisms suggested in studies of understory communities in other forests. Our results suggest that high-N additions can decrease plant diversity in tropical forests, but that this response may vary with rate of N addition.

Effects of experimental nitrogen additions on plant diversity in tropical forests of contrasting disturbance regimes in southern China

Responses of understory plant diversity to nitrogen (N) additions were investigated in reforested forests of contrasting disturbance regimes in southern China from 2003 to 2008: disturbed forest (withharvesting of understory vegetation and litter) and rehabilitated forest (without harvesting). Experimental additions of N were administered as the following treatments: Control, 50 kg N ha1yr1, and 100kg N ha1yr1. Nitrogen additions did not significantly affect understory plant richness, density,and cover in the disturbed forest. Similarly, no significant response was found for canopy closure in thisforest. In the rehabilitated forest, species richness and density showed no significant response to Nadditions; however, understory cover decreased significantly in the N-treated plots, largely a functionof a significant increase in canopy closure. Our results suggest that responses of plant diversity to N deposition may vary with different land-use history, and rehabilitated forests may be more sensitive to N deposition.

Prospective study of exclusive strontium-/yttrium-90 beta-irradiation of primary and recurrent pterygia with no prior surgical excision. Clinical outcome of long-term follow-up

PURPOSE: To evaluate the consecutive treatment results regarding pterygium recurrence and the efficacy of exclusive strontium-/yttrium-90 beta-irradiation for primary and recurrent pterygia and to analyze the functional outcome. PATIENTS AND METHODS: Between October 1974 and December 2005, 58 primary and 21 recurrent pterygia were exclusively treated with strontium-/yttrium-90 beta-irradiation with doses ranging from 3,600 to 5,500 cGy. The follow-up time was 46.6 +/- 26.7 months, with a median of 46.5 months. RESULTS: The treatment led to a size reduction in all pterygia (p < 0.0001). Neither recurrences nor side effects were observed during therapy and follow-up in this study. Best-corrected visual acuity increased (p = 0.0064). Corneal astigmatism was reduced in recurrent pterygia (p = 0.009). CONCLUSION: Exclusive strontium-/yttrium-90 beta-irradiation of pterygia is a very efficient and well-tolerated treatment, with remarkable aesthetic and rehabilitative results in comparison to conventional treatments, especially for recurrent lesions which have undergone prior surgical excision.

Short-term response of the Ca cycle of a montane forest in Ecuador to low experimental CaCl 2 additions

The tropical montane forests of the E Andean cordillera in Ecuador receive episodic Sahara-dust inputs particularly increasing Ca deposition. We added CaCl2 to isolate the effect of Ca deposition by Sahara dust to tropical montane forest from the simultaneously occurring pH effect. We examined components of the Ca cycle at four control plots and four plots with added Ca (2 × 5 kg ha–1 Ca annually as CaCl2) in a random arrangement. Between August 2007 and December 2009 (four applications of Ca), we determined Ca concentrations and fluxes in litter leachate, mineral soil solution (0.15 and 0.30 m depths), throughfall, and fine litterfall and Al concentrations and speciation in soil solutions. After 1 y of Ca addition, we assessed fine-root biomass, leaf area, and tree growth. Only < 3% of the applied Ca leached below the acid organic layer (pH 3.5–4.8). The added CaCl2 did not change electrical conductivity in the root zone after 2 y. In the second year of fertilization, Ca retention in the canopy of the Ca treatment tended to decrease relative to the control. After 2 y, 21% of the applied Ca was recycled to soil with throughfall and litterfall. One year after the first Ca addition, fine-root biomass had decreased significantly. Decreasing fine-root biomass might be attributed to a direct or an indirect beneficial effect of Ca on the soil decomposer community. Because of almost complete association of Al with dissolved organic matter and high free Ca2+ : Al3+ activity ratios in solution of all plots, Al toxicity was unlikely. We conclude that the added Ca was retained in the system and had beneficial effects on some plants.

Stereoselectivity of Additions to N-Methyl Acetonitrilium Fluorosulfonate

Alkoxy-N-methyl-acetiminium salts were prepared by addition of CH3OH and C2H5OH to N-methyl acetonitrilium fluorosulfonate at low temperature. Analysis of the (5)J(HH) and (3)J(13)C-H coupling constants in the NMR spectra showed an anti addition with a diastereoselectivity of >9596. Deprotonation of these salts with (Z)-configuration gave the corresponding N-methyl-alkoxyacetimines with very high (E)-configuration. Upon protonation at -78 degrees C, these iminoesters gave the corresponding alkoxy-N-methyl-acetirninium salts with (E)-configuration. Computational analyses of the iminoesters and the corresponding iminium cations including the conformations give insight into the relative stability. Nitrilium salts can be used as reagents, exemplified by some esterifications between simple acids and alcohols.

Nutrient additions affecting matter turnover in forest and pasture ecosystems

Nutrient inputs into ecosystems of the tropical mountain rainforest region are projected to further increase in the next decades. To investigate whether important ecosystem services such as nutrient cycling and matter turnover in native forests and pasture ecosystems show different patterns of response, two nutrient addition experiments have been established: NUMEX in the forest and FERPAST at the pasture. Both ecosystems already responded 1.5 years after the start of nutrient application (N, P, NP, Ca). Interestingly, most nutrients remained in the respective systems. While the pasture grass was co-limited by N and P, most tree species responded to P addition. Soil microbial biomass in the forest litter layer increased after NP fertilization pointing to nutrient co-limitation. In pasture soils, microorganisms were neither limited by N nor P. The results support the hypothesis that multiple and temporally variable nutrient limitations can coexist in tropical ecosystems.