Origin of needle fibre calcite (NFC) : a geochemical approach

ABSTRACTNeedle fibre calcite (NFC) is one of the most widespread habits of pedogenic calcite. It is a monocrystal of calcite, in the shape of a needle, with a diameter of one micron and a length between 4 and 103 times its width. NFC occurs in soils with different macroscopic and microscopic morphologies. Macroscopically, two main habits of NFC exist: "cotton ball'Mike clusters and as "powder" coating on pebbles inside the soil. It can also act as nucleation sites for precipitation of calcite cements of purely physicochemical origin (LCC - Late Calcitic Cement). Although many studies have been conducted on needle fibre calcite, its origin remains a subject of debate. The NFC having never been reproduced in the laboratory whatever the considered approach, the processes responsible for its precipitation as a so particular morphology remain unexplained. The shift between the length orientation of the needle crystal and the normal axis of calcite growth (c-axis) is also unresolved.Samples taken in two soils observed in quarries (Villiers and Savagnier) in the Swiss Jura Mountains are used to investigate the processes involved in the formation of these calcite crystals in pedogenic environments. Three groups of microscopic morphologies are distinguished: (i) simple needles (SN), (ii) simple needles with overgrowths (SNO), and (iii) simple needles with nanofibres (SNN), nanofibres being either organic or mineral in nature. These groups correspond to different stages in the formation and evolution of NFC.Comparison of carbon and oxygen isotope compositions of NFC with LCC, in relationship with the composition of the carbonate host rock (CHR), and the carbon isotope signature of dissolved inorganic carbon (DIC) from the soil waters, indicates that both NFC and LCC are precipitated in isotopic equilibrium with the soil solution. Similar Ô13C and Ô180 values of the elongated NFC and the rhombohedral calcite crystals of the LCC suggest that the precipitation of these different calcite habits is not due to changes in physicochemical conditions. The growth of NFC crystals inside an organic mould formed by the fungal hyphae could explain the formation of calcite ciystals in the shape of a needle in isotopic equilibrium with the local environment.Strontium and calcium isotope compositions of the three microscopic groups of NFC and LCC were also studied, in order to determine the origin of calcium (Ca2+) entrapped in the calcite lattice and to elucidate the processes responsible for the precipitation of NFC. The 87Sr/86Sr ratio of the SN is closer to the 87Sr/86Sr ratio of the carbonate host rock than the LCC, SNO, and SNN. This could be another clue for the formation of SN inside fungal hyphae, because fungi are known to dissolve the rocks to release and translocate through their hyphae nutrients necessary for their growth. SN and SNN are depleted in Sr and enriched in ^Ca compared to the LCC. In the context of Villiers quarry, where the two ciystal shapes precipitate at similar temperature (in a range of 0,6°C), such variations are the result of a slower precipitation rate of NFC, which is inconsistent with a purely physicochemically precipitated elongate crystal.Finally, NFC is enriched in major and trace elements (i.e. Fe, Zn, Cu, and Mo) compared to the LCC. This enrichment is ascribed to modification in precipitation processes between the NFC and LCC. Right now, it is not possible to preclude the influence of the particular shape of NFC or the biological influence. REEs are not fractionated in NFC, contrary to LCC. Thus, NFC does not precipitate from a percolation solution circulating downward the soil, which should lead to the fractionation of the REEs. As explained above, fungi, are able to dissolve and translocate nutrients. This kind of processes allows releasing elements in the soil solution without fractionation and could explain the particular chemical signature of NFC regarding the REEs.The geochemical approach to investigate the origin of NFC presented in this study does not allow providing direct clues to the fungal origin of NFC, but brings several new insights in the understanding of the formation of such a particular mineral, calcite needles, by precluding definitively their physicochemical origin.RESUMELa calcite en aiguilles (NFC) est l'une des formes les plus ubiquiste de calcite pédogénique. Il s'agit d'un monocrystal de calcite d'un diamètre d'un micron et d'une longueur 4 à 102 fois supérieure à sa largeur. A l'échelle macroscopique, la NFC a été observée sous deux principaux aspects : l'une « cotonneuse » et l'autre formant un mince croûte autour des graviers du sol. La NFC peut également servir de support à la nucléation de ciments secondaires précipités de manière purement physico-chimique (LCC). Malgré les nombreuses études menées sur la NFC, son origine demeure encore inconnue. A ce jour, aucune expérience en laboratoire n'a permis de créer de la calcite en aiguilles, et ce, quelque soit l'approche abordée. Par conséquent, les processus précis responsables de la précipitation calcite avec une telle morphologie restent inconnus. Le décalage existant entre l'axe d'allongement des aiguilles de calcite et l'axe normal de croissance de la calcite (axe c) reste inexpliqué.Des échantillons de NFC, LCC, roche mère, eau de pluie des différents horizons du sol ont été prélevés principalement au front de deux carrières de graviers, ainsi que dans un profil de sol adjacent à ces carrières, dans le but de mieux comprendre les processus à l'origine de la précipitation de calcite en forme d'aiguille. Trois micro-morphologies ont été distinguées: les aiguilles simples (SN), les aiguilles simples avec surcroissances calcitiques (SNO) et enfin les aiguilles simples avec nanofibres (SNN), celles-ci pouvant être de minérales ou organiques. Ces groupes, d'après nos résultats et les études antérieures pourraient correspondre à différentes étapes de formation de la calcite en aiguilles.Dans un premier temps, la comparaison des signatures isotopiques de la calcite en aiguilles, du LCC, de la roche mère et du carbone inorganique dissout dans la solution du sol (CID) indique que la NFC, tout comme le LCC, précipite en équilibre avec la solution du sol. Les valeurs similaires en Ô13C et δ180 de cristaux de calcite allongés (NFC) et rhombohédriques (LCC) formés dans un même milieu suggère que ces différences morphologiques ne peuvent pas être attribuées à des modifications purement physico-chimiques. La croissance de NFC à l'intérieur d'un moule organique comme les hyphes de champignons semble être la seule hypothèse plausible permettant d'expliquer la formation de monocrystaux allongés de calcite en équilibre avec leur environnement.La composition isotopique en strontium (Sr) et calcium (Ca) des LCC et des trois micro¬morphologies de la NFC ont été étudiées également, afin de déterminer l'origine du Ca2+ présent dans le réseau cristallin de la calcite en aiguilles, ainsi que les processus responsables de la formation de NFC. Les valeurs du rapport 87Sr/86$r de la forme SN sont les plus proches de celles de la roche mère par rapport aux formes SNN et SNO et du LCC. Ceci pourrait être un nouvel indice de l'implication des champignons dans la précipitation de calcite en aiguilles, puisqu'ils sont connus pour avoir la capacité de dissoudre les roches afin de libérer les nutriments nécessaires à leur croissance, ainsi que de les transloquer par leurs hyphes. De plus, les formes SN et SNN sont appauvries en Sr et enrichies en "Ca, comparativement au LCC. Dans le sol étudié, tous les carbonates de calcium précipitent à la même température, par conséquent, de telles variations sont dues à un taux de précipitation plus lent de SN et SNN, ce qui est contradictoire avec l'hypothèse physico-chimique. Pour finir, la NFC est enrichie en certains éléments majeurs et traces (i.e. Fe, Zn, Cu et Mo) par rapport au LCC. Ceci peut être attribué à différents processus de formation entre la NFC et le LCC. Pour le moment il est impossible d'exclure l'influence de la forme particulière de la NFC ou celle du champignon. Les terres rares (REEs) ne sont pas fractionnées dans la NFC, contrairement au LCC. Ceci peut être expliqué par le fait que la NFC précipite à partir d'une solution qui n'a pas percolé à travers le sol. Les champignons en dissolvant les roches mettent en solution éléments sans les fractionner. L'approche géochimique de l'étude de la calcite en aiguilles ne permets pas de produire des preuves directes sur sa potentielle origine fongique, mais permet de mieux comprendre comment un minéral aussi singulier que la NFC peut se former. D'autre pare cette étude permets d'exclure définitivement l'hypothèse physico-chimique de l'origine de la calcite en aiguilles

Angioplastie primaire par voie radiale ou fémorale dans les STEMI

Introduction La stratégie de reperfusion coronarienne par voie percutanée (PCI: percutaneous coronary intervention) est considérée comme étant la méthode de choix dans la prise en charge urgente des STEMI(H). Actuellement, les deux accès artériels principaux pour les PCI sont l'artère fémorale et l'artère radiale. La voie radiale est préconisée en première intention par les guidelines actuelles car elle serait associée à moins de complications hémorragiques. Objectif L'objectif de cette étude était de comparer la voie d'abord radiale à la voie fémorale, chez les patients admis pour un STEMI, en analysant le succès de la procédure de revascularisation, l'évolution clinique et les complications. Méthode Il s'agit d'une étude observationnelle, comprenant 268 patients admis au CHUV entre le 1er janvier et le 31 décembre 2013, avec le diagnostic de STEMI. Le choix de la voie d'accès artériel (fémorale ou radiale) était laissé au cardiologue interventionnel, sans randomisation. Les patients ont été séparés en 2 groupes, selon la voie d'abord vasculaire choisie au début de la procédure de revascularisation (intention to treat). Les endpoints primaires étaient les saignements majeurs (≥ 3 selon BARC)(A), et le door to balloon time(B). Les endpoints secondaires étaient les MACE(C), les saignements mineurs(A), le taux succès des procédures(D), le temps de fluoroscopie, la quantité de produit de contraste, et le taux de crossover(E) Résultats 268 patients en STEMI ont été inclus dans cette étude, pour un geste de revascularisation en urgence. La moyenne d'âge était de 64.3 ans, avec 73.1% d'hommes. 3 cas de saignements majeurs(A) ont lieu avec la voie radiale (3.4%), et 10 avec la voie fémorale (5.6%), p=0.44. Le door to balloon time ne diffère pas de manière significative selon la voie d'accès employée : 42 min (34-57) pour le groupe radial, et 48 min (31-61) pour le groupe fémoral, p=0.09. Les taux de MACE étaient de 8.0% avec la voie radiale, et de 6.7% avec la voie fémorale, p=0.7. Le taux de crossover était de 4.5% avec la voie radiale, et 0.6% avec la voie fémorale, p=0.02. Le temps de fluoroscopie était de 7min 28sec (5min 9 sec - 12min 25) pour la voie fémorale, contre 12min 22sec (9min 30 sec - 16min 19sec) pour la voie radiale, p < 0.05. La quantité de produit de contraste nécessaire était de 120 ml (100-160) pour le groupe fémoral, et de 170 ml (140-210) pour le groupe radial, p < 0.05. Le taux de succès était comparable entres les 2 groupes : 97.7% pour le groupe radial et 96.0% pour le groupe fémoral, p=0.47. 5.7% des patients du groupe radial sont décédés, contre 5.7% du groupe fémoral, p=0.97. Conclusion Notre étude démontre que la prise en charge d'un STEMI par voie radiale est possible, puisqu'elle n'allonge pas le « door to balloon time », qu'elle n'augmente pas le taux de MACE ni les saignements majeurs, que soit au point de ponction ou non. Par contre la voie radiale augmente la quantité de produit de contraste nécessaire, et allonge le temps de fluoroscopie de manière non négligeable. De futures études permettront peut-être de mieux définir les groupes de patients qui pourraient bénéficier le plus d'une approche radiale.

Estudo polarográfico sobre a determinação de Fe(III) utilizando-se a técnica da polarografia de pulso diferencial

A differential pulse polarographic study with the objective to determine iron (III) in presense of copper (II) in a supporting electrolyte based on citrate - EDTA was made. The best experimental conditions found were a supporting electrolyte of citrate 0.25 mol L-1, EDTA 0.050 mol L-1 and KNO3 0.50 mol L-1, pH 5.00. In this media iron (III) showed a polarographic peak in -0.08 V and the copper (II) in -0.34 V, both vs. Ag/AgCl (saturated KCl). Thus, a analytical method was developed and applied to determine iron (III) in brass alloy, a matrix were copper is in large excess over iron. The results obtained showed no interference of copper in the iron determination. The value of 0.21% of iron in the sample alloy composition was obtained and the method was validated by atomic absortion and recovery test, and the results exhibited a good agreement with the proposed method.

Estudo arqueométrico de cerâmicas do Sítio Guará, Goiás, Brasil

There is no evidence of urban civilization in Brazilian prehistory; most inhabitants lived in tribal groupings, probably with regional economic integration among several independent tribes. There is little evidence of seasonal migrations between the coast and the inland of southern Brazil. Some specialized horticulturists competed among themselves but other groups lived more isolated and probably peacefully, in the upper interfluvial regions. Chemical analysis of artifacts is a means of documenting traffic in particular materials and intraregional production and distribution, development of craft specialization and typological refinement among other issues. In this study we tested some possibilities in two different cultural contexts using the parametric k0 neutron activation analysis technique, which allowed the determination of elements: Al, As, Au, Ce, Cl, Co, Cr, Cs, Cu, Fe, Ga, K, La, Na, Rb, Sc, Ta, Ti, V and Zn.

Complexos metálicos com o herbicida glifosato: revisão

We present studies involving metallic ions and the herbicide glyphosate. The metallic complexes of Cu(II), Zn(II), Mn(II), Ni(II), Cd(II), Pb(II), Cr(III), Fe(III), Co(III), ammonium, sodium, Ag(I), alkaline earth metals and of some lanthanides ions are described. The complexes are discussed in terms of their synthesis, identification, stability and structural properties, based on data from the current literature.

Estudo multivariado de solos urbanos da cidade de Teresina

The concentrations of Cu, Pb, Zn, Cr, Ni, Al, Mn and Fe were measured by atomic absorption spectrometry, of 19 topsoil samples collected in the Teresina city urban area to discriminate natural and anthropic contributions and identify possible sources of pollution. The average concentrations of Cu, Zn, Pb and Cr of the urban soils were 6.11, 8.56, 32.12 and 7,17 mg/kg-1, respectively. Statistical analysis techniques, such as principal component analysis (PCA) and hierarchical cluster analysis (HCA), were used to analyze the data. Mn, Ni and Cr levels were interpreted as natural contributions, whereas Pb, Zn and, in part, Cu were accounted for mainly by anthropic activities. High Pb levels were observed in the ancient avenues.

Classificação de água de coco processada e natural por meio de HCA, PCA e teores de íons metálicos determinados por ICP OES

Inductively Coupled Plasma Optical Emission Spectrometry was used to determine Ca, Mg, Mn, Fe, Zn and Cu in samples of processed and natural coconut water. The sample preparation consisted in a filtration step followed by a dilution. The analysis was made employing optimized instrumental parameters and the results were evaluated using methods of Pattern Recognition. The data showed common concentration values for the analytes present in processed and natural samples. Principal Component Analysis (PCA) and Hierarchical Cluster Analysis (HCA) indicated that the samples of different kinds were statistically different when the concentrations of all the analytes were considered simultaneously.

Avaliação da concentração de alguns íons metálicos em diferentes espécies de líquens do cerrado Sul-Mato-Grossense

Concentrations of Fe, Mn, Co, Cr, Zn and Cu were determinated using flame atomic absorption spectrometry in nine lichen species of the Sul-Mato-Grossense cerrado. The average metal ion concentrations varied in the following ranges: Fe, 248.41-1568.01; Mn, 98.50-397.33; Co, 10.08-24.81; Cr, 18.24-44.26; Zn, 14.62-34.79 and Cu, 3.23-7.57 mg kg-1. Statistical analysis (Pearson and Cluster) applied to the metal ion concentrations indicated that the accumulation of these ions can be due to several anthropogenic sources including agricultural activities, mineral exploration, biomass burning, soil mineral composition and leather tanning processes by chromium.

Classificação multivariada de ervas medicinais da Região Amazônica e suas infusões de acordo com sua composição mineral

In this study, the mineral composition of leaves and teas of medicinal plants was evaluated. Ca, Cu, Fe, Mg, Mn e Zn were determined in the samples using flame atomic absorption spectrometry. Principal component analysis was applied to discriminate the samples studied. The samples were divided within the 2 groups according to their mineral composition. Copper and iron were the variables that contributed most to the separation of the samples followed by Ca, Mg, Mn and Zn. The information in the principal component analysis was confirmed by the dendrogram obtained by hierarchical cluster analysis.

ANÁLISE EXPLORATÓRIA DAS CONCENTRAÇÕES DOS METAIS NA, CA, MG, SR E FE EM EXTRATO AQUOSO DE PETRÓLEO, DETERMINADOS POR ICP OES, APÓS OTIMIZAÇÃO EMPREGANDO PLANEJAMENTO DE EXPERIMENTOS

AbstractThe purpose of this study was to evaluate the best operating conditions of ICP OES for the determination of Na, Ca, Mg, Sr and Fe in aqueous extract of crude oil obtained after hot extraction with organic solvents (ASTM D 6470-99 modified). Thus, the full factorial design and central composite design were used to optimize the best conditions for the flow of nebulization gas, the flow of auxiliary gas, and radio frequency power. After optimization of variables, a study to obtain correct classification of the 18 samples of aqueous extract of crude oils (E1 to E18) from three production and refining fields was carried out. Exploratory analysis of these extracts was performed by principal component analysis (PCA), hierarchical cluster analysis (HCA) and linear discriminant analysis (LDA), using the original variables as the concentration of the metals Na, Ca, Mg, Sr and Fe determined by ICP OES.

AVALIAÇÃO DA BIOACUMULAÇÃO DE METAIS EM Cyprinus carpio PELA INTERAÇÃO COM SEDIMENTO E ÁGUA DE RESERVATÓRIO

Bioaccumulation of Ag, Al, Cd, Co, Cr, Cu, Fe, Mn, Ni, Pb and Zn was determined in the gills and liver of Cyprinus carpio and related to concentrations in the sediment and water of the Alagados Reservoir, Ponta Grossa/Paraná. Cd and Fe exceeded the legal limit for water. Fe was the most abundant metal in the reservoir's water and sediment. The metals in the sediment were below the level of probable adverse effects on biota. There were no significant differences between sampling sites for water and sediment. Liver and gills had higher concentrations of Al, Fe and Zn, with a significant increase in Al (P > 0.05) compared to the increase in weight and size of the specimens. Statistically, gills showed higher concentrations of Al, Cd, Co, Cr, Mn and Zn and liver higher concentrations of Cu and Fe. Co, Cu, Fe, Mn and Zn showed significant differences (P < 0.01) between the organs. The bioaccumulation factors (BAF) showed that the interaction of water with gills promotes greater accumulation of metals in this organ. Despite the low concentrations in the reservoir, bioaccumulation of metals in gills and liver of C. carpio occurs by its interaction with contaminated water and sediment, respectively.

Estudo da influência de adições de prata na resistividade elétrica da liga Cu-5%Al

Estudou-se a influência de adições de 2, 6 e 8% Ag, em peso, na resistividade elétrica da liga Cu-5%Al, utilizando-se o método dos quatro pontos e um sistema de registro contínuo de variação da resistividade elétrica com a temperatura. Os resultados obtidos indicaram que a resistividade elétrica da liga aumenta com o aumento da concentração de prata e que as inflexões observadas nas curvas de variação da resistividade com a temperatura de aquecimento podem ser atribuídas à solubilização da prata na matriz de Cu-Al. Observou-se também que a velocidade de aquecimento da amostra é um fator importante na intensidade e forma dos eventos observados.

Determinação das energias de ativação para nucleação de precipitados e difusão da prata na liga cu-2%al com adições de prata

As energias de ativação para nucleação de precipitados ricos em prata e de difusão da prata no cobre, em ligas de Cu-2%Al contendo 2, 4, 6, 8, 10 e 12%Ag, em peso, foram determinadas utilizando-se medidas de variação da microdureza com a temperatura e o tempo de envelhecimento. Os resultados indicaram que, com o método utilizado, é possível obter valores para as energias de ativação para nucleação da fase rica em prata e de difusão da prata no cobre bastante próximos daqueles citados na literatura.

Interaction study of moxifloxacin with Cu(II) ion using square-wave voltammetry and its application in the determination in tablets

This work presents an electroanalytical method for the determination of moxifloxacin (MOXI) in tablets by its interaction with Cu(II) ion and subsequent electrochemical reduction at hanging mercury drop electrode (HMDE). A well-defined reduction peak at -0.21 V vs. Ag/AgCl in Phosphate buffer 0.04 mol L-1 pH 8.0 was observed for the complex reduction MOXI-Cu(II), using square-wave voltammetry (SWV). Using a 10 s of accumulation time at -0.40 V was found a limit detection of 3.60x10-8 mol l-1. The obtained results have shown good agreement with those obtained by spectrophotometric method.

Cultivar, harvest year, and storage conditions affecting nutritional quality of common beans (Phaseolus vulgaris L.

Sixteen common bean cultivars were compared concerning the physicochemical characteristics of their raw seeds in the course of two consecutive harvests, as well as the effect of storage conditions on starch and dietary fiber content of cooked beans. Using cluster analysis it was possible to identify groups of cultivars with different nutritional features. Bean cultivars were categorized into four different groups according either to their macronutrient content (crude protein-PROT, total dietary fiber-TDF, insoluble dietary fiber-IDF, soluble dietary fiber-SDF, digestible starch-DS, and resistant starch-RS) or to their micronutrient levels (Fe, Zn, Mn, Cu, Ca, Mg, and P). Guateian 6662 and Rio Tibagi appeared to be the most suitable cultivars to prevent nutritional deficiencies, because they had high PROT, DS, Fe, and Zn content. The high total dietary fiber and RS content of Iraí, Minuano, and TPS Bonito cultivars, and specially the high soluble fiber content of Guateian 6662 and Rio Tibagi cultivars suggests that they could have a beneficial role in controlling blood lipid and glucose levels. Cooked beans had a decrease in DS and an increase in RS content after storage (4 °C or -20 °C), but these changes were more prominent in beans that had low RS content before cooking than in those of high RS content. TDF, IDF, and SDF did not change after storage.