Organic sulfur oxidation to sulfate in soil samples for total sulfur determination by turbidimetry

Sulfur in the soil occurs in two basic forms, organic and inorganic S. The organic form accounts for 95 % of S in most soils. The effectiveness of organic S to oxidate to sulfate was evaluated for total S determination in soil samples by wet (acid) and dry-ash (alkaline) oxidation methods. To evaluate the wet method and the possible use as a reference when evaluating the dry method proposed here, a reference standard from the US National Institute of Standards and Technology (NIST) was used (Montana Soil - NIST 2710). The dry-ash oxidation process with alkaline oxidizing agents is one of the simplest oxidation methods of organic S to the sulfate form and was compared with the wet process. The objective of the study was to develop a dry method that would be easy to apply and allow the complete conversion of organic S to sulfate in soil samples and later detection by turbidimetry. The effectiveness of organic S oxidation to sulfate was evaluated by means of three alkaline oxidation mixtures: NaHCO3 + Ag2O, Eschka mixture (17 % Na2CO3, 66 % MgO, and 17 % K2CO3), and NaHCO3 + CuO. The procedure to quantify the sulfate concentration was based on the reaction with barium chloride and turbidimetric detection. Sulfur quantification in the standard sample by the wet method proved adequate, precise and accurate. It should also be pointed out that no significant differences were found (95 % reliability) between the wet and dry processes (NaHCO3 and Ag2O oxidation mixture) in six different Brazilian soils. The proposed dry method can therefore be used in the preparation of soil samples for total S determination.

Perpendicular magnetic anisotropy in chemically disordered FePd-FeV(100) alloy thin films

We find that the use of V(100) buffer layers on MgO(001) substrates for the epitaxy of FePd binary alloys yields to the formation at intermediate and high deposition temperatures of a FePd¿FeV mixed phase due to strong V diffusion accompanied by a loss of layer continuity and strong increase of its mosaic spread. Contrary to what is usually found in this kind of systems, these mixed phase structures exhibit perpendicular magnetic anisotropy (PMA) which is not correlated with the presence of chemical order, almost totally absent in all the fabricated structures, even at deposition temperatures where it is usually obtained with other buffer layers. Thus the observed PMA can be ascribed to the V interdiffusion and the formation of a FeV alloy, being the global sample saturation magnetization also reduced.

Size effects in the magneto-optical response of Co nanoparticles

A study of the magneto-optical (MO) spectral response of Co nanoparticles embedded in MgO as a function of their size and concentration in the spectral range from 1.4 to 4.3 eV is presented. The nanoparticle layers were obtained by sputtering at different deposition temperatures. Transmission electron microscopy measurements show that the nanoparticles have a complex structure which consists of a crystalline core having a hexagonal close-packed structure and an amorphous crust. Using an effective-medium approximation we have obtained the MO constants of the Co nanoparticles. These MO constants are different from those of continuous Co layers and depend on the size of the crystalline core. We associate these changes with the size effect of the intraband contribution to the MO constants, related to a reduction of the relaxation time of the electrons into the nanoparticles.

Evolução quantitativa de planossolos do agreste do estado de Pernambuco

A pedogênese dos solos planossólicos, especialmente da região do Agreste de Pernambuco, tem sido pouco estudada, havendo indicações e dúvidas relativas a alguns aspectos como a possível dualidade ou retrabalhamentos diferenciados na formação do material de origem, total das perdas e ganhos e a relativa mobilidade dos principais elementos constitutivos durante a evolução dos solos. Foram estudados três solos com marcantes contrastes texturais em uma topossequência da região. Foram estudados três solos com marcantes contrastes texturais em uma topossequência no Agreste de Pernambuco. Os objetivos da pesquisa foram averiguar a compatibilidade dos solos com os materiais geológicos subjacentes e avaliar quantitativamente as perdas e os ganhos ocorridos durante a pedogênese. Para isso foram realizadas análises química total e de zircônio (Zr) e quartzo, tomados como base para determinação de um índice de intemperização, em todos os horizontes dos solos e no material de origem. Verificou-se que os solos são constituídos por materiais autóctones, com apenas pequenas indicações de retrabalhamento dos materiais mais superficiais. Durante o processo de intemperização ou pedogênese, verificou-se perda de, aproximadamente, 50 % do peso original do solo. As perdas referentes aos principais elementos constituintes dos solos apresentaram a seguinte ordem: MgO > CaO > Fe2O3 > Al2O3 > SiO2. Os nítidos contrastes texturais, devido à argilização dos horizontes Bt, parecem ser principalmente resultado de uma combinação de outros processos, que não simples eluviação-iluviação.

APLICAÇÃO SUPERFICIAL DE CALCÁRIO COM DIFERENTES TEORES DE MAGNÉSIO E GRANULOMETRIAS EM SISTEMA PLANTIO DIRETO

RESUMO A correção da acidez do solo no sistema plantio direto (SPD) é feita por meio da aplicação de calcário na superfície sem incorporação. Com a hipótese de que a fonte e granulometria dos corretivos interferem na velocidade de reação no solo em curto prazo e na resposta das culturas à calagem na superfície em SPD, foram realizados dois experimentos, sendo um em Latossolo Vermelho Distrófico textura muito argilosa e outro em Neossolo Litólico Húmico textura franco-arenosa, no período de 2010 a 2012. O delineamento empregado, em cada experimento, foi em blocos completos ao acaso, no esquema fatorial 2 × 2 × 4, com três repetições. Os tratamentos foram constituídos de duas fontes de calcário, calcítico (25-50 g kg-1 MgO) e dolomítico (160-180 g kg-1 MgO), duas faixas de poder relativo de neutralização total (PRNT), faixa B (PRNT de 60 a 75 %) e faixa D (PRNT>90 %), e quatro doses de calcário na superfície, sendo um tratamento-controle sem calagem e três doses estimadas para elevar a saturação por bases do solo (0,00-0,20 m), a 50, 70 e 90 %. Nos dois experimentos, o calcário foi aplicado a lanço sobre a superfície do solo, em agosto de 2010. Realizaram-se dois cultivos em 2010/11 e 2011/12, com milho e soja, no Latossolo Vermelho Distrófico, e soja e milho, no Neossolo Litólico Húmico, respectivamente. A aplicação superficial de calcário nos dois solos, após 12 meses, proporcionou redução da acidez na camada de 0,00-0,05 m e, em menor grau, na de 0,05-0,10 m. A amenização da acidez nas camadas da superfície foi mais acentuada com o emprego de doses mais elevadas de calcário calcítico e de corretivo com granulometria mais fina. A calagem superficial aumentou as concentrações de Ca-foliar com a utilização de calcário calcítico e de Mg-foliar com o uso de calcário dolomítico, e reduziu os teores foliares de Mn e Zn, independentemente da fonte de calcário, nas culturas de milho e soja. As produtividades de grãos de milho e soja no Latossolo Vermelho Distrófico e Neossolo Litólico Húmico aumentaram com as doses de calcário, mas não foram influenciadas pelas fontes e faixas de PRNT dos corretivos. A calagem superficial é uma prática efetiva e importante para maximizar a produtividade de grãos das culturas em SPD, independentemente do teor de Mg e da granulometria dos corretivos.

Measures of ionicity of alkaline-earth oxides from the analysis of ab initio cluster wave functions

We present an analysis of the M-O chemical bonding in the binary oxides MgO, CaO, SrO, BaO, and Al2O3 based on ab initio wave functions. The model used to represent the local environment of a metal cation in the bulk oxide is an MO6 cluster which also includes the effect of the lattice Madelung potential. The analysis of the wave functions for these clusters leads to the conclusion that all the alkaline-earth oxides must be regarded as highly ionic oxides; however, the ionic character of the oxides decreases as one goes from MgO, almost perfectly ionic, to BaO. In Al2O3 the ionic character is further reduced; however, even in this case, the departure from the ideal, fully ionic, model of Al3+ is not exceptionally large. These conclusions are based on three measures, a decomposition of the Mq+-Oq- interaction energy, the number of electrons associated to the oxygen ions as obtained from a projection operator technique, and the analysis of the cation core-level binding energies. The increasing covalent character along the series MgO, CaO, SrO, and BaO is discussed in view of the existing theoretical models and experimental data.

Rigorous characterization of oxygen vacancies in ionic oxides

Charged and neutral oxygen vacancies in the bulk and on perfect and defective surfaces of MgO are characterized as quantum-mechanical subsystems chemically bonded to the host lattice and containing most of the charge left by the removed oxygens. Attractors of the electron density appear inside the vacancy, a necessary condition for the existence of a subsystem according to the atoms in molecules theory. The analysis of the electron localization function also shows attractors at the vacancy sites, which are associated to a localization basin shared with the valence domain of the nearest oxygens. This polyatomic superanion exhibits chemical trends guided by the formal charge and the coordination of the vacancy. The topological approach is shown to be essential to understand and predict the nature and chemical reactivity of these objects. There is not a vacancy but a coreless pseudoanion that behaves as an activated host oxygen.

Efeito da fertilização com fósforo, potássio e magnésio em jacatupé infectado com rizóbio em um Latossolo álico

Com o objetivo de avaliar o efeito da fertilização com fósforo, potássio e magnésio na fixação do N2 em jacatupé (Pachyrhizus erosus (L.) Urban) cultivado em um Latossolo Amarelo distrófico álico da Zona da Mata de Pernambuco, foi conduzido um experimento inoculando as sementes com a estirpe de Bradyrhizobium sp. NFB 450. Foram aplicadas quatro fórmulas de adubação com potássio e magnésio, na proporção (K2O:MgO) 2:1, em quantidades crescentes (0:0, 40:20, 60:30 e 80:40 kg ha-1 de K2O e MgO, respectivamente) e cinco níveis de fósforo (0, 20, 40, 60 e 80 kg ha-1 de P2O5, na forma de superfosfato triplo). A produção máxima foi obtida quando aplicou-se 64 kg ha-1 de P2O5. Observou-se efeito significativo para os níveis de K2O-MgO, quando em comparação com o tratamento sem K e Mg; entretanto, com o aumento da aplicação verificou-se diminuição da produção de matéria seca e do N total, e aumento do P total acumulado na parte aérea. O jacatupé respondeu a níveis baixos da fertilização com P, K e Mg, e mostrou-se efetivo na fixação do N2, com grande potencial na produção de biomassa.

X-Ray Diffraction Studies of Soils and Soil Stabilizers, HR-106, 1965

The two goals of this project stated in the Proposal were: (1) study lime diffusion in clayey soils, and (2) find the role of MgO in soil-dolomitic lime stabilization. Because of the practice significance of these goals we temporarily overstaffed this project, giving somewhat a "crash" program. As a result, proposed work was finished up early (as were the funds), and more important, some of the findings were early enough and of sufficient merit to put into field trials in the Fall of 1964. The work now being completed and the funds all being expended, this Final Report is therefore submitted before the anticipated project termination date.

Produtividade e componentes da produção do amendoim da seca em razão da época de semeadura e da aplicação de cálcio

Este trabalho teve por objetivo estudar o efeito do calcário, como fornecedor de cálcio, em diferentes épocas de semeadura, na cultura do amendoim cultivar Tatu, sobre os componentes da produção e a produtividade de vagens em semeadura na época considerada seca. O experimento foi conduzido em um Latossolo Vermelho-Escuro, argiloso, em Selvíria, MS. Foram estudadas quatro épocas de semeadura do amendoim da seca (21/1, 4/2, 18/2 e 4/3), combinadas com quatro doses de Ca (0, 45, 90 e 135 kg ha-1 de Ca), aplicadas no sulco de semeadura, usando como fonte calcário dolomítico com PRNT de 90,1% e com teores de 21% de CaO e 18% de MgO. Foram avaliados o número de vagens por planta, o número de grãos por vagem e por planta, o peso de 100 grãos, o rendimento e a produtividade das vagens. Conclui-se que: 1) à medida que se atrasa a semeadura, há a probabilidade de ocorrer deficiência hídrica nos períodos vegetativo e reprodutivo, reduzindo a produtividade do amendoim da seca; 2) há boa produtividade de vagens quando a semeadura é realizada até o início do mês de fevereiro; 3) a resposta do amendoim da seca ao Ca é baixa em solos onde inicialmente se tem alto teor de Ca e saturação por bases considerada média, principalmente, quando a disponibilidade hídrica também é um fator limitante; 4) a aplicação de calcário no sulco de semeadura como meio de fornecimento de Ca para a cultura do amendoim é uma prática viável.

Igneous layering, fractional crystallization and growth of granitic plutons: The Dolbel batholith in SW Niger

This study reassesses the development of compositional layering during the growth of granitic plutons, with emphasis on fractional crystallization and its interaction with both injection and inflation-related deformation. The Dolbel batholith (SW Niger) consists of 14, kilometre-sized plutons emplaced by pulsed magma inputs. Each pluton has a coarse-grained core and a peripheral layered series. Rocks consist of albite (An(<= 11)), K-feldspar (Or(96 99), Ab(1) (4)), quartz, edenite (X(Mg)=0337-0.55), augite (X(Mg)=0.65-0.72) and accessories (apatite, titanite and Fe-Ti-oxides). Whole-rock compositions are metaluminous, sodic (K(2)O/Na(2)O=0.49-0.62) and iron-rich [FeO(tot)/(FeO(tot)+MgO)=0.65-0.82]. The layering is present as size-graded and modally graded, sub-vertical, rhythmic units. Each unit is composed of three layers, which are, towards the interior: edenite +/- plagioclase (C(a/p)), edenite+plagioclase+augite+quartz (C(q)), and edenite+plagioclase+augite+quartz+K-feldspar (C(k)). All phases except quartz show zoned microstructures consisting of external intercumulus overgrowths, a central section showing oscillatory zoning and, in the case of amphibole and titanite, complexly zoned cores. Ba and Sr contents of feldspars decrease towards the rims. Plagioclase crystal size distributions are similar in all units, suggesting that each unit experienced a similar thermal history. Edenite, characteristic of the basal C(a/p) layer, is the earliest phase to crystallize. Microtextures and phase diagrams suggest that edenite cores may have been brought up with magma batches at the site of emplacement and mechanically segregated along the crystallized wall, whereas outer zones of the same crystals formed in situ. The subsequent C(q) layers correspond to cotectic compositions in the Qz-Ab-Or phase diagram at P(H2O)=5 kbar. Each rhythmic unit may therefore correspond to a magma batch and their repetition to crystallization of recurrent magma recharges. Microtextures and chemical variations in major phases allow four main crystallization stages to be distinguished: (1) open-system crystallization in a stirred magma during magma emplacement, involving dissolution and overgrowth (core of edenite and titanite crystals); (2) in situ fractional crystallization in boundary layers (C(a/p) and C(q) layers); (3) equilibrium `en masse' eutectic crystallization (C(k) layers); (4) compaction and crystallization of the interstitial liquid in a highly crystallized mush (e. g. feldspar intercumulus overgrowths). It is concluded that the formation of the layered series in the Dolbel plutons corresponds principally to in situ differentiation of successive magma batches. The variable thickness of the Ck layers and the microtextures show that crystallization of a rhythmic unit stops and it is compacted when a new magma batch is injected into the chamber. Therefore, assembly of pulsed magma injections and fractional crystallization are independent, but complementary, processes during pluton construction.

Comparison of Various Commercial Hydrated Limes for Reducing Soil Plasticity, HR-82 and HR-106, 1964

Atterberg limits tests were performed on mixtures of gumbotil soil and the various chief chemical compounds found in hydrated limes. The results were then checked with commercial hydrated limes of varying chemical compositions. Results indicate that among the major constituents of hydrated limes Ca(OH)2 is most effective in reducing soil plasticity. MgO shows a moderate effect, but Mg(OH)2 and CaCO3 show practically no effect. There is, however, practically no difference between different types or between the same type of commercial hydrated limes for the reduction of soil plasticity. The choice of lime for soil-lime stabilization should, therefore, be dictated by the relative price and pozzolanic strength characteristics of the lime.

The Role of Magnesium in Concrete Deterioration, HR-355, Appendix, 1994

In the main report concerning the role that magnesium may have in highway concrete aggregate, over 20,000 electron microprobe data were obtained, primarily from automated scans, or traverses, across dolomite aggregate grains and the adjacent cement paste. Representative traverses were shown in figures and averages of the data were presented in Table II. In this Appendix, detailed representative and selected analyses of carbonate aggregate only are presented. These analyses were not presented in the main report because they would be interesting to only a few specialists in dolomite· rocks. In this Appendix, individual point analyses of mineral compositions in the paste have been omitted along with dolomite compositions at grain boundaries and cracks. Clay minerals and quartz inclusions in the aggregate are also not included. In the analyses, the first three column headings from left to right show line number, x-axis, and y-axis (Line number is an artifact of the computer print-out for each new traverse. Consecutive line numbers indicate a continuous traverse with distances between each point of 1.5 to a few μ-m. X-axis and y-axis are coordinates on the electron microscope stage). The next columns present weight percent oxide content of FeO, K20, CaO, Si02, Al203, MgO, SrO, BaO, MnO, Na20, and C02 (calculated assuming the number of moles of C02 is equal to the sum of moles of oxides, chiefly CaO and MgO), TOTAL (the sum of all oxides), and total (sum of all oxides excluding COi). In many of the analyses total is omitted.

Polymers as carriers for rhizobial inoculant formulations

The aim of this work was to evaluate the efficiency of carboxymethyl cellulose (CMC) and starch blends as carrier materials of rhizobial inoculants regarding their capacity to maintain viable cells and promote cowpea (Vigna unguiculata) nodulation. The experimental design adopted was completely randomized, with three replicates. Forty different compositions of carboxymethyl cellulose (CMC) with starch, compatibilized or not with different proportions of MgO or ZnO, were evaluated regarding their ability of maintaining rhizobial viable cells during the storage period of one month at room temperature, in an initial screening. Thereafter, selected inoculant carrier blends were evaluated regarding their ability to maintain viable rhizobial cells for a period of 165 days, and their performance as inoculant carriers was compared to a peat-based inoculant carrier under greenhouse conditions. Rhizobial cells were better maintained in blends containing 50-60% CMC. Compatibilizing agents did not increase survival of rhizobial cells for 30 days of storage. The cowpea nodulation of polymer blends was statistically the same of peat-based inoculants. CMC/starch polymer blends are efficient carriers to rhizobial inoculants for up to 165 days of storage, when compatibilized with MgO (1%).

Caracterizacion quimica de la vidriera del roseton del Duomo de Siena (Italia, 1288-1289)

Se han caracterizado químicamente una colección de vidrios arquitectónicos coloreados originales del rosetón del Duomo (catedral) de Siena, Italia, realizados bajo diseño del artista Duccio di Buoninsegna en 1288-89. Esta comunicación expone los resultados obtenidos mediante el empleo de microsonda electrónica de Castaing (mayoritarios) y espectrometría de masas con fuente de plasma acoplado inductivamente (ICP-MS, elementos en traza) en vidrios de varios colores (incoloro, verde oscuro, verde oliva, amarillo, violeta, rosa, azul oscuro, azul celeste, rojo plaqué). Se trata de vidrios sódico-cálcicos (valores en peso alrededor del 13-14 % de Na2O, 56-64 % SiO2, 4% MgO, 9-10 % CaO, 2,5-4 K2O) de tradición por tanto mediterránea. Un resultado semejante se encontró precedentemente para vidrios realizados a lo largo del siglo XIV, cuanto menos unos 40 años después (vidriera de la iglesia del Monestir de Pedralbes, Barcelona). En general, el estado de conservación de estos vidrios es bueno, excepto por lo que se refiere a la adherencia de las grisallas al vidrio base.