Alkali- and nitrate-free synthesis of highly active Mg-Al hydrotalcite-coated alumina for FAME production

Mg-Al hydrotalcite coatings have been grown on alumina via a novel alkali- and nitrate-free impregnation route and subsequent calcination and hydrothermal treatment. The resulting Mg-HT/AlO catalysts significantly outperform conventional bulk hydrotalcites prepared via co-precipitation in the transesterification of C-C triglycerides for fatty acid methyl ester (FAME) production, with rate enhancements increasing with alkyl chain length. This promotion is attributed to improved accessibility of bulky triglycerides to active surface base sites over the higher area alumina support compared to conventional hydrotalcites wherein many active sites are confined within the micropores. © 2014 The Royal Society of Chemistry.

Novel Ni-Mg-Al-Ca catalyst for enhanced hydrogen production for the pyrolysis-gasification of a biomass/plastic mixture

A Ni-Mg-Al-Ca catalyst was prepared by a co-precipitation method for hydrogen production from polymeric materials. The prepared catalyst was designed for both the steam cracking of hydrocarbons and for the in situ absorption of CO2 via enhancement of the water-gas shift reaction. The influence of Ca content in the catalyst and catalyst calcination temperature in relation to the pyrolysis-gasification of a wood sawdust/polypropylene mixture was investigated. The highest hydrogen yield of 39.6molH2/g Ni with H2/CO ratio of 1.90 was obtained in the presence of the Ca containing catalyst of molar ratio Ni:Mg:Al:Ca=1:1:1:4, calcined at 500°C. In addition, thermogravimetric and morphology analyses of the reacted catalysts revealed that Ca introduction into the Ni-Mg-Al catalyst prevented the deposition of filamentous carbon on the catalyst surface. Furthermore, all metals were well dispersed in the catalyst after the pyrolysis-gasification process with 20-30nm of NiO sized particles observed after the gasification without significant aggregation.

Metales activados de Rieke: parte II; síntesis de Zn*, Cu*, Al*, In* y Ni* y de compuestos orgánicos y organometálicos

En este artículo de la revisión se describen las diferentes rutas para la formación de metales activados de Reike, en particular Zn*, Cu*' Al*, In* y Ni*. Se describe también la síntesisde compuestos orgánicos y organometálicos obtenidos mediante estos metales.

Evaluation of Femtosecond Laser-Induced Breakdown Spectroscopy for Analysis of Animal Tissues

The aim of this work was to evaluate the performance of femtosecond laser-induced breakdown spectroscopy (fs-LIBS) for the determination of elements in animal tissues. Sample pellets were prepared from certified reference materials, such as liver, kidney, muscle, hepatopancreas, and oyster, after cryogenic grinding assisted homogenization. Individual samples were placed in a two-axis computer-controlled translation stage that moved in the plane orthogonal to a beam originating from a Ti:Sapphire chirped-pulse amplification (CPA) laser system operating at 800 mu and producing a train of 840 mu J and 40 fs pulses at 90 Hz. The plasma emission was coupled into the optical fiber of a high-resolution intensified charge-coupled device (ICCD)-echelle spectrometer. Time-resolved characteristics of the laser-produced plasmas showed that the best results were obtained with delay times between 80 and 120 ns. Data obtained indicate both that it is a matrix-independent sampling process and that fs-LIBS can be used for the determination of Ca, Cu, Fe, K, Mg, Na, and P, but efforts must be made to obtain more appropriate detection limits for Al, Sr, and Zn.

First stars XIV. Sulfur abundances in extremely metal-poor stars

Context. Precise S abundances are important in the study of the early chemical evolution of the Galaxy. In particular the site of the formation remains uncertain because, at low metallicity, the trend of this alpha-element versus [Fe/H] remains unclear. Moreover, although sulfur is not bound significantly in dust grains in the ISM, it seems to behave differently in DLAs and old metal-poor stars. Aims. We attempt a precise measurement of the S abundance in a sample of extremely metal-poor stars observed with the ESO VLT equipped with UVES, taking into account NLTE and 3D effects. Methods. The NLTE profiles of the lines of multiplet 1 of S I were computed with a version of the program MULTI, including opacity sources from ATLAS9 and based on a new model atom for S. These profiles were fitted to the observed spectra. Results. We find that sulfur in EMP stars behaves like the other alpha-elements, with [S/Fe] remaining approximately constant below [Fe/H] = -3. However, [S/Mg] seems to decrease slightly with increasing [Mg/H]. The overall abundance patterns of O, Na, Mg, Al, S, and K are most closely matched by the SN model yields by Heger & Woosley. The [S/Zn] ratio in EMP stars is solar, as also found in DLAs. We derive an upper limit to the sulfur abundance [S/Fe] < +0.5 for the ultra metal-poor star CS 22949-037. This, along with a previously reported measurement of zinc, argues against the conjecture that the light-element abundance pattern of this star (and by analogy, the hyper iron-poor stars HE 0107-5240 and HE 1327-2326) would be due to dust depletion.

Chemical evolution of the Galactic bulge as traced by microlensed dwarf and subgiant stars IV. Two bulge populations

Based on high-resolution (R approximate to 42 000 to 48 000) and high signal-to-noise (S/N approximate to 50 to 150) spectra obtained with UVES/VLT, we present detailed elemental abundances (O, Na, Mg, Al, Si, Ca, Ti, Cr, Fe, Ni, Zn, Y, and Ba) and stellar ages for 12 new microlensed dwarf and subgiant stars in the Galactic bulge. Including previous microlensing events, the sample of homogeneously analysed bulge dwarfs has now grown to 26. The analysis is based on equivalent width measurements and standard 1-D LTE MARCS model stellar atmospheres. We also present NLTE Li abundances based on line synthesis of the (7)Li line at 670.8 nm. The results from the 26 microlensed dwarf and subgiant stars show that the bulge metallicity distribution (MDF) is double-peaked; one peak at [Fe/H] approximate to -0.6 and one at [Fe/H] approximate to +0.3, and with a dearth of stars around solar metallicity. This is in contrast to the MDF derived from red giants in Baade's window, which peaks at this exact value. A simple significance test shows that it is extremely unlikely to have such a gap in the microlensed dwarf star MDF if the dwarf stars are drawn from the giant star MDF. To resolve this issue we discuss several possibilities, but we can not settle on a conclusive solution for the observed differences. We further find that the metal-poor bulge dwarf stars are predominantly old with ages greater than 10 Gyr, while the metal-rich bulge dwarf stars show a wide range of ages. The metal-poor bulge sample is very similar to the Galactic thick disk in terms of average metallicity, elemental abundance trends, and stellar ages. Speculatively, the metal-rich bulge population might be the manifestation of the inner thin disk. If so, the two bulge populations could support the recent findings, based on kinematics, that there are no signatures of a classical bulge and that the Milky Way is a pure-disk galaxy. Also, recent claims of a flat IMF in the bulge based on the MDF of giant stars may have to be revised based on the MDF and abundance trends probed by our microlensed dwarf stars.

First stars XII. Abundances in extremely metal-poor turnoff stars, and comparison with the giants

Context. The detailed chemical abundances of extremely metal-poor (EMP) stars are key guides to understanding the early chemical evolution of the Galaxy. Most existing data, however, treat giant stars that may have experienced internal mixing later. Aims. We aim to compare the results for giants with new, accurate abundances for all observable elements in 18 EMP turno. stars. Methods. VLT/UVES spectra at R similar to 45 000 and S/N similar to 130 per pixel (lambda lambda 330-1000 nm) are analysed with OSMARCS model atmospheres and the TURBOSPECTRUM code to derive abundances for C, Mg, Si, Ca, Sc, Ti, Cr, Mn, Co, Ni, Zn, Sr, and Ba. Results. For Ca, Ni, Sr, and Ba, we find excellent consistency with our earlier sample of EMP giants, at all metallicities. However, our abundances of C, Sc, Ti, Cr, Mn and Co are similar to 0.2 dex larger than in giants of similar metallicity. Mg and Si abundances are similar to 0.2 dex lower (the giant [Mg/Fe] values are slightly revised), while Zn is again similar to 0.4 dex higher than in giants of similar [Fe/H] (6 stars only). Conclusions. For C, the dwarf/giant discrepancy could possibly have an astrophysical cause, but for the other elements it must arise from shortcomings in the analysis. Approximate computations of granulation (3D) effects yield smaller corrections for giants than for dwarfs, but suggest that this is an unlikely explanation, except perhaps for C, Cr, and Mn. NLTE computations for Na and Al provide consistent abundances between dwarfs and giants, unlike the LTE results, and would be highly desirable for the other discrepant elements as well. Meanwhile, we recommend using the giant abundances as reference data for Galactic chemical evolution models.

Evaluation of grinding methods for pellets preparation aiming at the analysis of plant materials by laser induced breakdown spectrometry

It has been demonstrated that laser induced breakdown spectrometry (LIBS) can be used as an alternative method for the determination of macro (P, K. Ca, Mg) and micronutrients (B, Fe, Cu, Mn, Zn) in pellets of plant materials. However, information is required regarding the sample preparation for plant analysis by LIBS. In this work, methods involving cryogenic grinding and planetary ball milling were evaluated for leaves comminution before pellets preparation. The particle sizes were associated to chemical sample properties such as fiber and cellulose contents, as well as to pellets porosity and density. The pellets were ablated at 30 different sites by applying 25 laser pulses per site (Nd:YAG@1064 nm, 5 ns, 10 Hz, 25J cm(-2)). The plasma emission collected by lenses was directed through an optical fiber towards a high resolution echelle spectrometer equipped with an ICCD. Delay time and integration time gate were fixed at 2.0 and 4.5 mu s, respectively. Experiments carried out with pellets of sugarcane, orange tree and soy leaves showed a significant effect of the plant species for choosing the most appropriate grinding conditions. By using ball milling with agate materials, 20 min grinding for orange tree and soy, and 60 min for sugarcane leaves led to particle size distributions generally lower than 75 mu m. Cryogenic grinding yielded similar particle size distributions after 10 min for orange tree, 20 min for soy and 30 min for sugarcane leaves. There was up to 50% emission signal enhancement on LIBS measurements for most elements by improving particle size distribution and consequently the pellet porosity. (C) 2011 Elsevier B.V. All rights reserved.

Variation in the Distribution of Trace Elements in Renal Cell Carcinoma

The development of cancer is a complex, multistage process during which a normal cell undergoes genetic changes that result in phenotypic alterations and in the acquisition of the ability to invade other sites. Inductively coupled plasma optical emission spectroscopy was used to estimate the contents of Al, Ca, Cd, Cr, Cu, Fe, K, Mg, Mn, Na, P, Pb, and Zn in healthy kidney and renal cell carcinoma (RCC), and significant differences were found for all elements. Along with the progression of the malignant disease, a progressive decrease of Cd and K was observed. In fact, for Cd, the concentration in stage T4 was 263.9 times lower than in stage T1, and for K, the concentration in stage T4 was 1.73 times lower than in stage T1. Progressive accumulation was detected for P, Pb, and Zn in stage T4. For P, the concentration in stage T4 was 11.1 times higher than in stage T1; for Pb, the concentration in stage T4 was 232.7 times higher than in T1; and for Zn, the concentration in T4 was 8.452 times higher than in T1. This study highlights the marked differences in the concentrations of selected trace metals in different malignant tumor stages. These findings indicate that some trace metals may play important roles in the pathogenesis of RCC.

Simultaneous optimization by neuro-genetic approach for analysis of plant materials by laser induced breakdown spectroscopy

A simultaneous optimization strategy based on a neuro-genetic approach is proposed for selection of laser induced breakdown spectroscopy operational conditions for the simultaneous determination of macronutrients (Ca, Mg and P), micro-nutrients (B, Cu, Fe, Mn and Zn), Al and Si in plant samples. A laser induced breakdown spectroscopy system equipped with a 10 Hz Q-switched Nd:YAG laser (12 ns, 532 nm, 140 mJ) and an Echelle spectrometer with intensified coupled-charge device was used. Integration time gate, delay time, amplification gain and number of pulses were optimized. Pellets of spinach leaves (NIST 1570a) were employed as laboratory samples. In order to find a model that could correlate laser induced breakdown spectroscopy operational conditions with compromised high peak areas of all elements simultaneously, a Bayesian Regularized Artificial Neural Network approach was employed. Subsequently, a genetic algorithm was applied to find optimal conditions for the neural network model, in an approach called neuro-genetic, A single laser induced breakdown spectroscopy working condition that maximizes peak areas of all elements simultaneously, was obtained with the following optimized parameters: 9.0 mu s integration time gate, 1.1 mu s delay time, 225 (a.u.) amplification gain and 30 accumulated laser pulses. The proposed approach is a useful and a suitable tool for the optimization process of such a complex analytical problem. (C) 2009 Elsevier B.V. All rights reserved.

Determination of Cr, Fe, Co, Ni, Cu, Zn, As and Pb in liquid chemical waste by energy dispersive X-ray fluorescence

A method for simultaneous determination of Cr, Fe, Co, Ni, Cu, Zn, As e Pb in liquid chemical waste using Energy Dispersive X-Ray Fluorescence (EDXRF) technique was evaluated. A small sample amount (200 mu L) was dried on a 6.35 mu m thickness Mylar film at 60 degrees C and the analyses were carried out using an EDXRF spectrometer operated with an X-ray Mo tube (Zr filter) at 30 kV/20 mA. The acquisition time was 300 s and the Ga element was utilized as internal standard at 25 mg/L for quantitative analysis. The method trueness was assessed by spiking and the detection limit for those elements ranged from 0.39 to 1.7 mg/L. This method is notable because it assists the choice of the more appropriated waste treatment procedure, in which inter elemental interference is a matter of importance. In addition, this inexpensive method allows a non-destructive determination of the elements from (19)K to (92)U simultaneously.

Exploring the emission intensities of ICP OES aided by chemometrics in the geographical discrimination of mineral waters

A rapid method for classification of mineral waters is proposed. The discrimination power was evaluated by a novel combination of chemometric data analysis and qualitative multi-elemental fingerprints of mineral water samples acquired from different regions of the Brazilian territory. The classification of mineral waters was assessed using only the wavelength emission intensities obtained by inductively coupled plasma optical emission spectrometry (ICP OES), monitoring different lines of Al, B, Ba, Ca, Cl, Cu, Co, Cr, Fe, K, Mg, Mn, Na, Ni, P, Pb, S, Sb, Si, Sr, Ti, V, and Zn, and Be, Dy, Gd, In, La, Sc and Y as internal standards. Data acquisition was done under robust (RC) and non-robust (NRC) conditions. Also, the combination of signal intensities of two or more emission lines for each element were evaluated instead of the individual lines. The performance of two classification-k-nearest neighbor (kNN) and soft independent modeling of class analogy (SIMCA)-and preprocessing algorithms, autoscaling and Pareto scaling, were evaluated for the ability to differentiate between the various samples in each approach tested (combination of robust or non-robust conditions with use of individual lines or sum of the intensities of emission lines). It was shown that qualitative ICP OES fingerprinting in combination with multivariate analysis is a promising analytical tool that has potential to become a recognized procedure for rapid authenticity and adulteration testing of mineral water samples or other material whose physicochemical properties (or origin) are directly related to mineral content.

Zn uptake, physiological response and stress attenuation in mycorrhizal jack bean growing in soil with increasing Zn concentrations

The influence of arbuscular mycorrhizal fungi (AMF) inoculation on Canavalia ensiformis growth. nutrient and Zn uptake, and on some physiological parameters in response to increasing soil Zn concentrations was studied. Treatments were applied in seven replicates in a 2 x 4 factorial design, consisting of the inoculation or not with the AMF Glomus etunicatum, and the addition of Zn to soil at the concentrations of 0, 100, 300 and 900 mg kg(-1). AMF inoculation enhanced the accumulation of Zn in tissues and promoted biomass yields and root nodulation. Mycorrhizal plants exhibited relative tolerance to Zn up to 300 mg kg(-1) without exhibiting visual symptoms of toxicity, in contrast to non-mycorrhizal plants which exhibited a significant growth reduction at the same soil Zn concentration. The highest concentration of Zn added to soil was highly toxic to the plants. Leaves of plants grown in high Zn concentration exhibited a Zn-induced proline accumulation and also an increase in soluble amino acid contents; however proline contents were lower in mycorrhizal jack beans. Plants in association or not with the AMF exhibited marked differences in the foliar soluble amino acid profile and composition in response to Zn addition to soil. In general, Zn induced oxidative stress which could be verified by increased lipid peroxidation rates and changes in catalase, ascorbate peroxidase, glutathione reductase and superoxide dismutase activities. In summary, G. etunicatum was able to maintain an efficient symbiosis with jack bean plants in moderately contaminated Zn-soils, improving plant performance under those conditions, which is likely to be due to a combination of physiological and nutritional changes caused by the intimate relation between fungus and plant. The enhanced Zn uptake by AMF inoculated jack bean plants might be of interest for phytoremediation purposes. (C) 2009 Elsevier Ltd. All rights reserved.

Reclaimed wastewater: Impact on soil-plant system under tropical conditions

This study investigated the ionic speciation of reclaimed urban wastewater (RWW), and the impact of increasing RWW irrigation rates on soil properties and plant nutrition under field conditions. Most RWW elements (>66%) are readily available as NH(4)(+), Ca(2+), Mg(2+), K(+), SO(4)(2-), Cl(-), H(3)BO(3), Mn(2+) and Zn(2+), but in imbalanced proportion for plant nutrition. Lead, Cd, Cr and Al in RWW are mostly bounded with DOM or OH. Irrigation with RWW decreased soil acidity, which is beneficial to the acidic tropical soil. Although RWW irrigation builds exchangeable Na(+) up, the excessive Na(+) was leached out of the soil profile after a rainy summer season (>400 mm). Benefits of the disposal of RWW to the soil under tropical conditions were discussed, however, the over irrigation with RWW (>100% of crop evapotranspiration) led to a nutritional imbalance, accumulating S and leading to a plant deficiency of P and K. (C) 2011 Elsevier B.V. All rights reserved.