991 resultados para Ni-Zn-Sm ferrite
Resumo:
To evaluate the extent of human impact on a pristine Antarctic environment, natural baseline levels of trace metals have been established in the basement rocks of the Larsemann Hills, East Antarctica. From a mineralogical and geochemical point of view the Larsemann Hills basement is relatively homogeneous, and contains high levels of Pb, Th and U. These may become soluble during the relatively mild Antarctic summer and be transported to lake waters by surface and subsurface melt water. Melt waters may also be locally enriched in V, Cr, Co, Ni, Zn and Sri derived from weathering of metabasite pods. With a few notable exceptions, the trace metal concentrations measured in the Larsemann Hills lake waters can be entirely accounted for by natural processes such as sea spray and surface melt water input. Thus, the amount of trace metals released by weathering of basement lithologies and dispersed into the Larsemann Hills environment, and presumably in similar Antarctic environments, is, in general, not negligible, and may locally be substantial. The Larsemann Hills sediments are coarse-grained and contain minute amounts of clay-size particles, although human activities have contributed to the generation of fine-grained material at the most impacted sites. Irrespective of their origin, these small amounts of fine-grained clastic sediments have a relatively small surface area and charge, and are not as effective metal sinks as the abundant, thick cyanobacterial algal mats that cover the lake floors. Thus, the concentration of trace metals in the Larsemann Hills lake waters is regulated by biological activity and thawing-freezing cycles, rather than by the type and amount of clastic sediment supply. (c) 2005 Elsevier Ltd. All rights reserved.
Resumo:
In this PhD study, the effects of the cation substitutions on the physical properties of pyroxenes have been discussed. The results of this work extend the knowledge on pyroxenes with different chemical compositions. These properties might be used in the development of ceramic pigments, advanced materials and for the mineralogical phase identification. First of all, the crystallographic differences between Ge and Si pyroxenes have been examined. The structure of C2/c Ca rich Ge clinopyroxenes is very close to the low pressure C2/c structural configuration found in Ca-rich Si-pyroxenes. The shear of the unit cell is very similar, and the difference between a Ge end member and the corresponding Si-rich one is less than 1°. Instead, a remarkable difference exists between Ca-poor Si and Ge clinopyroxenes. First, Ca-poor Ge pyroxenes do not display a P21/c symmetry, but retain the C2/c symmetry; second, the observed C2/c structure shows, at room pressure, the configuration with highly kinked tetrahedral chains characteristic of the high pressure C2/c symmetry of Si Ca-poor pyroxenes. In orthopyroxenes, with Pbca symmetry, Ge-pyroxenes have volume larger than Si-pyroxenes. Samples along the system CaCoGe2O6 - CoCoGe2O6 have been synthesized at three different temperatures: 1050 °C, 1200 °C and 1250 °C. The aim of these solid state syntheses was to obtain a solid solution at ambient pressure, since the analogues Si-system needs high pressure. Unfortunately, very limited solution occurs because the structure forms of the two end member (high temperature for CaCoGe2O6 and high pressure CoCoGe2O6) are incompatible. The phase diagram of this system has been sketched and compared to that of Si. The cobalt end member (CoCoGe2O6) is stable at ambient pressure in two symmetries: at 1050 °C C2/c and 1200 °C Pbca. The impurity phase formed during these experiments is cobalt spinel. Raman spectroscopy has been used to investigate the vibrational properties of Ca-pyroxenes CaCoGe2O6, CaMgGe2O6, CaMgSi2O6 and CaCoSi2O6. A comparison between silicate and germanate pyroxenes shows significant changes in peak positions of the corresponding modes caused mainly by the difference of the Ge-Si atomic weight along with the distortion and compression of the coordination polyhedra. Red shift in Raman spectra of germanates has been calculated by a rough scale factor calculated by a simple harmonic oscillator model, considering the different bond lengths for 4-coordinated Si ~ 1.60- 1.65 Å vs Ge–O distance ~1.70 - 1.80 Å. The Raman spectra of CaMgGe2O6 and CaCoGe2O6 have been classified, in analogy with silicate (Wang et al., 2001) counterparts, in different ranges: - R1 (880-640 cm-1): strong T-O stretching modes of Ge and non-bridging O1 and O2 atoms within the GeO4 tetrahedron; - R2 (640-480 cm-1): stretching/bending modes of Ge-Obr-Ge bonds (chain stretching and chain bending); - R4 (480-360 cm-1): O-Ge-O vibrations; - R3 (360-240 cm-1): motions of the cations in M2 and M1 sites correlated with tetrahedral chain motion and tilting tetrahedra; - R5 (below 240 cm-1): lattice modes. The largest shift with respect to CaMgSi2O6 - CaCoSi2O6 is shown by the T-O stretching and chain modes. High-pressure Raman spectroscopy (up to about 8 GPa) on the same samples of Ca-pyroxenes using an ETH-type diamond anvil cell shows no phase transition within the P-ranges investigated, as all the peak positions vary linearly as a function of pressure. Our data confirm previous experimental findings on Si-diopside (Chopelas and Serghiou, 2000). In the investigated samples, all the Raman peaks shift upon compression, but the major changes in wavenumber with pressure are attributed to the chain bending (Ge-Obr-Ge bonds) and tetrahedra stretching modes (Ge-Onbr). Upon compression, the kinking angle, the bond lengths and T-T distances between tetrahedra decrease and consequently the wavenumber of the bending chain mode and tetrahedra stretching mode increases. Ge-pyroxenes show the higher P-induced peak-position shifts, being more compressible than corresponding silicates. The vibrational properties of CaM2+Ge2O6 (M2+ =Mg, Mn, Fe, Co, Ni, Zn) are reported for the first time. The wavenumber of Ge-Obr-Ge bending modes decreases linearly with increasing ionic radius of the M1 cation. No simple correlation has been found with M1 atomic mass or size or crystallographic parameters for the peak at ~850 cm-1 and in the low wavenumber regions. The magnetic properties of the system CaCoSi2O6 - CoCoSi2O6 have been investigated by magnetometry. The join is always characterized by 1 a.p.f.u. of cobalt in M1 site and this causes a pure collinear antiferromagnetic behaviour of the intra-chain superexchange interaction involving Co ions detected in all the measurements, while the magnetic order developed by the cobalt ions in M2 site (intra-chain) is affected by weak ferromagnetism, due to the non-collinearity of their antiferromagnetic interaction. In magnetically ordered systems, this non-collinearity effect promotes a spin canting of anti-parallel aligned magnetic moments and thus is a source of weak ferromagnetic behaviour in an antiferromagnetic. The weak ferromagnetism can be observed only for the samples with Co content higher than 0.5 a.p.f.u. in M2, when the concentration is sufficiently high to create a long range order along the M2 chain which is magnetically independent of M1 chain. The ferromagnetism was detected both in the M(T) at 10 Oe and M(H).
Resumo:
Bedrock geochemical analysis, coupled with detailed data analysis, was carried out on some 260 samples taken from two areas of 'the Harlech Dome, near Dolgellau, North Wales. This was done to determine if rocks from mineralised and non-mineralised areas could be distinguished, and to determine mineralisation types and wall rock alterations. The Northern Area, near Talsarnau, has no recorded mineralisation, while the Southern Area, near Bontddu, has been exploited for gold. The rocks sampled, in both areas, were from the Cambrian Gamlan Flags, Clogau Shales, Vigra Flags, later vein materials, and igneous intrusions. All samples were analysed, using a new rapid, atomic absorption spectrophotometric technique, for Si, AI, Fe, Cu, Ni, Zn, Pb, Sr, Hg, and Ba. In addition 60 samples were analysed by X-ray fluorescence for Mn, Ti, Ca, K, Na, P, Cr, Ce, La, S, Y , Rh, and Th. Total CO2 was determined, on selected samples, using a combustion technique. Elemental distributions, for each rock type, in each area, were· plotted, and means, standard deviations, and enrichment indices were calculated. Multivariate statistical analysis on the results distinguished a Cu-type mineralisation in the Northern area, and both Cu and Pb/Zn types in the Southern Area. It also showed the Northern Area to be less strongly mineralised than the Southern one in which both mineralisation types are associated with wall rock alteration. Elemental associations and trends due to sedimentary processes were distinguished from those related to mineralisation. Hg is related to mineralisation, and plots of factor scores, on the sampling grid, produced clusters of mineralisation related factors in areas of known mineralisation. A double Fourier Trend Analysis program, with a wavelength search routine, was developed and used to recognise sedimentary trends for Sr. Y., Rb, and Th. These trends were interpreted to represent areas of low pH and reducing conditions. They also indicate that the supply of sediment remained constant over Gamlan, Clogau, and Vigra times. The trend surface of Hg showed no association with rock type. It is shown that analysis of a small number of samples, for a carefully selected number of elements, with detailed data analysis, can provide more useful information than analysis of a large number of samples for many elements. The mineralisation is suggested to have been the result of water solutions leaching ore metals from the sedimentary rocks and redepositing them in veins.
Resumo:
A concentração de seis elementos: Cd, Cr, Pb, Ni, Zn e Fe foi medida em sessenta e sete amostras de sumos de fruta 100 %, duas amostras de refrigerantes, dez amostras de concentrados de sumos e sete amostras de águas de diluição utilizadas no processamento dos sumos. As amostras de sumos representam numa prespectiva bastante abrangente o mercado Português de sumos de fruta 100 %. Os refrigerantes concentrados e águas de diluição foram cedidos por duas empresas fabricantes de sumos Portuguesas. As concentrações elementares foram medidas pelas técnicas de FAAS e GFAAS e foi medido também o grau Brix dos sumos. Os factores: fruta, percentagem de fruta, origem, agricultura, tratamento, embalagem, conservação e processo foram obtidos por informação do fabricante nos rótulos dos produtos e por contacto directo. Caracterizou-se o mercado em termos da concentração desses elementos e
caracterizou-se a sua diluição comparando-a com valores de referência do mercado Europeu. Mediu-se o grau de associação entre os diversos parâmetros e a concentração final elementar dos sumos e utilizou-se a análise de agrupamentos, a análise de correspondência múltipla e a análise factorial para reestruturar a matriz de dados. Dos resultados obtidos, os sumos de fruta apresentam a seguinte ordem de grandeza nas suas concentrações elementares: Cd
Resumo:
Nickel-containing catalysts are developed to oligomerize light olefins. Two nickel-containing zincosilicates (Ni-CIT-6 and Ni-Zn-MCM-41) and two nickel-containing aluminosilicates (Ni-HiAl-BEA and Ni-USY) are synthesized as catalysts to oligomerize propylene into C3n (C6 and C9) products. All catalysts oligomerize propylene, with the zincosilicates demonstrating higher average selectivities to C3n products, likely due to the reduced acidity of the Zn heteroatom.
To test whether light alkanes can be incorporated into this oligomerization reaction, a supported homogeneous catalyst is combined with Ni-containing zincosilicates. The homogeneous catalyst is included to provide dehydrogenation/hydrogenation functions. When this tandem catalyst system is evaluated using a propylene/n-butane feed, no significant integration of alkanes are observed.
Ni-containing zincosilicates are reacted with 1-butene and an equimolar propylene/1-butene mixture to study other olefinic feeds. Further, other divalent metal cations such as Mn2+, Co2+, Cu2+, and Zn2+ are exchanged onto CIT-6 samples to investigate stability and potential use for other reactions. Co-CIT-6 oligomerizes propylene, albeit less effectively than Ni-CIT-6. The other M-CIT-6 samples, while not able to oligomerize light olefins, may be useful for other reactions, such as deNOx.
Molecular sieves are synthesized, characterized, and used to catalyze the methanol-to-olefins (MTO) reaction. The Al concentration in SSZ-13 samples is varied to investigate the effect of Al number on MTO reactivity when compared to a SAPO-34 sample with only isolated Si Brønsted acid sites. These SSZ-13 samples display reduced transient selectivity behavior and extended reaction lifetimes as Si/Al increases; attributable to fewer paired Al sites. MTO reactivity for the higher Si/Al SSZ-13s resembles the SAPO-34 sample, suggesting that both catalysts owe their stable reaction behavior to isolated Brønsted acid sites.
Zeolites CHA and RHO are prepared without the use of organic structure-directing agents (OSDAs), dealuminated by steam treatments (500°C-800°C), and evaluated as catalysts for the MTO reaction. The effects of temperature and steam partial pressure during steaming are investigated. X-ray diffraction (XRD) and Ar physisorption show that steaming causes partial structural collapse of the zeolite, with degradation increasing with steaming temperature. 27Al MAS NMR spectra of steamed materials reveal the presence of tetrahedral, pentacoordinate, and hexacoordinate aluminum.
Proton forms of as-synthesized CHA (Si/Al=2.4) and RHO (Si/Al=2.8) rapidly deactivate under MTO testing conditions (400°C, atmospheric pressure). CHA samples steamed at 600°C performed best among samples tested, showing increased olefin selectivities and catalyst lifetime. Acid washing these steamed samples further improved activity. Reaction results for RHO were similar to CHA, with the RHO sample steamed at 800°C producing the highest light olefin selectivities. Catalyst lifetime and C2-C3 olefin selectivities increase with increasing reaction temperature for both CHA-type and RHO-type steamed samples.
Resumo:
This project describes a methodology optimization that would allow for a more efficient microwave assisted digestion process for petroleum samples. With the possible chance to vary various factors at once to see if any one factor was significant enough in the answers, experimental planning was used. Microwave assisted digestion allows, through the application of potency, an increasing number of collisions between the HNO3 and H2O2 molecules, favoring sample opening for complex matrixes. For this, a 24 factorial experimental planning was used, varying potency, time and the volumes for HNO3 65% and H2O2 30%. To achieve the desired answers, several elements were monitored (C, Cu, Cr, Fe, Ni, Zn and V) through Inductively coupled plasma atomic emission spectroscopy (ICP-OES). With this initial study it was noticed that the HNO3 was not a significant factor for any of the statistical studies for any of the analytes and the other 3 factors and their interactions showed statistical significance. A Box Behnken experimental planning was used taking in consideration 3 factors: H2O2 volume, time (min) and Potency (W), Nitric Acid kept at 4mL for a mass of 0,1g of petroleum. The results were extremely satisfying showing higher efficiency in the digestion process and taking in a responsibility between the answers for each analyte and the carbon monitoring was achieved in the following conditions: 7mL of H2O2, 700 Watts of potency and a reaction time of 7 minutes with 4mL de HNO3 for a mass of 0,1g of petroleum. The optimized digestion process was applied to four different petroleum samples and the analytes determined by ICP-OES
Resumo:
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.
Resumo:
Adsorption of Ni(2+), Zn(2+) or Pb(2+) by dry biomass of Arthrospira (Spirulina) platensis and Chlorella vulgaris was studied as a function of contact time and initial metal concentration. The zero point of charge calculated for these biosorbents (pH(zpc) 4.0 and 3.4, respectively) and additional pH tests suggested the use of pH in the range 5.0-5.5 for the experiments. The equilibrium isotherms were evaluated in terms of maximum sorption capacity and sorption affinity. The pseudo first and second order kinetic models were considered to interpret the experimental data, and the latter best described the adsorption system. Both the Freundlich and Langmuir models were shown to well describe the sorption isotherms, thus suggesting an intermediate mono/multilayer sorption mechanism. Compared to A. platensis (q(e) = 0.354, 0.495 and 0.508 mmol g(-1) for Ni(2+), Pb(2)+ and Zn(2+), respectively), C. vulgaris behaved as a better biosorbent because of higher equilibrium sorption capacity (q(e) = 0.499, 0.634 and 0.664 mmol g(-1), respectively). The removal efficiency decreased with increasing metal concentration, pointing out a passive adsorption process involving the active sites on the surface of the biomasses. The FT-IR spectroscopy evidenced that ions removal occurred mainly by interaction between metal and carboxylate groups present on both the cell walls. (C) 2011 Elsevier B.V. All rights reserved.
Resumo:
The title pendent-arm macrocyclic hexaamine ligand binds stereospecifically in a hexadentate manner, and we report here its isomorphous Ni-II and Zn-II complexes (both as perchlorate salts), namely (cis-6,13-dimethyl-1,4,8,11-tetraazacyclotetradecane-6,13-diamine-kappa(6)N)nickel(II) diperchlorate, [Ni(C12H30N6)](ClO4)(2), and (cis-6,13-dimethyl-1,4,8,11-tetraazacyclotetradecane-6,13-diamine-kappa(6)N)zinc(II) diperchlorate, [Zn(C-12 H30N6)](ClO4)(2). Distortion of the N-M-N valence angles from their ideal octahedral values becomes more pronounced with increasing metal-ion size and the present results are compared with other structures of this ligand.
Resumo:
Esta pesquisa foi desenvolvida na Plataforma Continental Amazônica (PCA) no trecho compreendido entre os cabos Orange (AP) e Maguari (PA), para determinar os teores de Zn, Co e Ni nos sedimentos superficiais, identificando o papel dos sedimentos como fonte ou reserva de elementos-traço. A concentração dos elementos metálicos apresentou a seguinte associação: Zn > Ni > Co. Os sedimentos localizados na PCA podem ser considerados como sítio de ocorrência natural dos elementos metálicos, não havendo influência de fontes poluidoras na liberação destes para o sistema.
Resumo:
Os resíduos gerados em domicílios incluem diversos produtos, como pesticidas, produtos farmacêuticos, detergentes, óleos de cozinha, metais pesados contidos em baterias e outros utensílios. Esses resíduos são lançados continuamente em aterro sanitário ou lixões em cidades como Manaus. O chorume produzido nesses aterros, quando não tratados, contamina recursos hídricos superficiais e subterrâneos. Neste estudo foi feita uma avaliação das conseqüências da liberação do chorume no sistema hídrico da bacia do Tarumã-Açu. Amostras de água e sedimento foram coletadas nos igarapés Matrinxã, Acará, Bolívia, bacia do Tarumã-Açu e dentro do aterro sanitário (Manaus - Amazonas - Brasil) em março 2001. As amostras de água foram filtradas em filtro Milipore (0,45 mm de poro) e, em seguida, tratadas com HNO3 concentrado. As amostras de sedimento foram peneiradas em malha de 0,053 mm e digeridas com HCl:HNO3 (1:3) a 150ºC. As concentrações de alguns metais pesados (Co, Cu, Fe, Cr, Ni, Mn, Pb e Zn) foram determinadas nas amostras de água e sedimento por espectrometria de absorção atômica de chama. Os resultados revelaram que a concentração dos metais pesados é muito acima dos permitidos pela resolução 357/2005 do CONAMA em praticamente todos os locais amostrados, mostrando que o Aterro Sanitário é um dos principais responsáveis pelo impacto ambiental observado nos corpos hídricos estudados. As análises dos componentes principais (PCA) e hierárquica de cluster (HCA), revelam que os pontos de coleta localizados dentro do aterro sanitário apresentam características diferentes dos outros locais amostrados. Além disso, o HCA e PCA mostraram que existe uma similaridade entre os pontos de coleta localizados fora do aterro o que permite afirmar que o chorume do aterro se dissolve por todo corpo hídrico estudado.
Resumo:
Em experimento de casa de vegetação, realizado em Campinas (SP), no período de janeiro a maio de 1980, estudaram-se os efeitos da peletização do lodo de esgoto, nas doses 0, 1 e 5% (v/v) do material seco, na produção de matéria seca e na absorção de Zn, Cu e Ni pela parte aérea do milho (Zea mays L.), em latossolo roxo (LR), latossolo vermelho-escuro (LE) e latossolo vermelho-amarelo (LV), que receberam ou não adição de CaCO3 suficiente para elevação do pH em água para 6,0. O experimento foi realizado em vasos com dois litros de capacidade, delineados em blocos ao acaso, com três repetições, e os tratamentos arranjados num esquema fatorial. Após 200 dias de incubação dos solos com o lodo e CaCO3, cultivaram-se quatro plantas de milho em cada vaso. A parte aérea foi quantificada 56 dias após a germinação, sendo cortada, seca, pesada e analisada para os elementos Zn, Cu e Ni. Amostras de terra de cada tratamento foram retiradas e tiveram os metais extraídos pelo DTPA. A peletização do lodo de esgoto resultou em diminuição significativa na produção de matéria seca pela parte aérea do milho, nos três solos estudados, em comparação com o lodo não peletizado. A adição de CaCO3 proporcionou aumento significativo na produção de matéria seca do milho apenas nos dois solos mais ácidos (LE e LV) e diminuiu o acúmulo de Zn na parte aérea desse vegetal cultivado no LE, sem distinção quanto ao tipo de lodo aplicado, não se observando diferenças significativas na absorção de Ni, em todos os solos analisados. A incorporação do lodo peletizado , que continha 19% menos Zn e Ni que o não peletizado, resultou em menor absorção de Zn, Cu e Ni nos três solos, exceto para o Ni no LR. Para todos os solos investigados, o método do DTPA mostrou-se mais adequado em prognosticar as quantidades disponíveis de Zn e de Cu para o milho, independentemente do tipo de lodo de esgoto aplicado e da elevação ou não do pH do solo pela adição de CaCO3.
Resumo:
Metais pesados formam um grupo de elementos com particularidades relevantes e de ocorrência natural no ambiente, como elementos acessórios na constituição de rochas. Esses elementos, apesar de associados à toxidez, exigem tratamento diferenciado em relação aos xenobióticos, uma vez que diversos metais possuem essencialidade (Fe, Mn, Cu, Zn e Ni) e benefício (Co) comprovados para as plantas. Nesse contexto, o objetivo deste trabalho foi determinar os teores naturais dos metais Fe, Mn, Zn, Ni, Cu e Co nos solos de referência de Pernambuco. Foram coletadas amostras de solo nas três regiões fisiográficas (Zona da Mata, Agreste e Sertão), dos dois primeiros horizontes dos 35 solos de referência do Estado de Pernambuco. A digestão das amostras baseou-se no método 3051A (USEPA, 1998), e a determinação foi efetuada em ICP-OES. Correlações significativas foram estabelecidas entre os metais e entre estes e a fração argila do solo, em ambos os horizontes, indicando a associação comum da maioria dos metais com solos mais argilosos. A maioria dos solos apresentou teores de Fe, Mn, Zn, Cu, Ni e Co menores que os de solos de outras regiões do País, com litologia mais máfica, o que corrobora o fato de que os teores desses elementos são mais diretamente relacionados aos minerais Fe-magnesianos. Os resultados indicam baixo potencial dos solos de Pernambuco em liberar Cu, Co e Ni para plantas, enquanto deficiências de Zn, Fe e Mn são menos prováveis. Os teores naturais de Fe, Mn, Zn, Cu, Ni e Co determinados podem ser utilizados como base para definição dos Valores de Referência de Qualidade para os solos de Pernambuco, de acordo com o preconizado pela legislação nacional.
Resumo:
Adsorption of Cu(II), Ni(II), Pb(II) and Zn(II) ions from aqueous solutions by N-(3,4-dihydroxybenzyl) chitosan have been carried out. The Langmuir (L), Freundlich (F), Langmuir - Freundlich (LF), Redlich-Peterson (RP) and Tóth (T) adsorption isotherms models have been applied to fit the experimental data. Nonlinear regression computational program "Enzefitte", which is a library of the more commonly used adsorption isotherm equations for obtaining tabular outuput suitable for plotting theoretical of fitted isotherms, has been used to estimate the adsorption parameters. These parameters were used to calculate the amount adsorbed q calc., a function of concentration (C).