Influence of basic properties of Mg,Al-mixed oxides on their catalytic activity in knoevenagel condensation between benzaldehyde and phenylsulfonylacetonitrile

The catalytic performance of Mg,Al-mixed oxides (MO20, MO25 and MO33) derived from hydrotalcites was evaluated in the Knoevenagel reaction between benzaldehyde and phenylsulfonylacetonitrile at 373 and 383 K. The best results were obtained for the sample MO20 that presented the highest basic sites density and external area and the smallest crystallite sizes. The relative amount of basic sites with weak to intermediate strength also played an important role on catalytic performance. By increasing the catalyst content from 1 to 5 wt.% at 383 K, a complete conversion of the reactants is attained, producing α-phenylsulfonylcinnamonitrile with a selectivity of 100%.

Síntese, caracterização e avaliação catalítica de Vo x/Mg yAlo x na reação de decomposição do isopropanol

Vanadium oxide supported on hydrotalcite-type precursors was studied in the decomposition of isopropanol. Hydrotalcite-type compounds with different y = Mg+2/Al+3 ratios were synthesized by the method of coprecipitating nitrates of Mg+2 and Al+3 cations with K2CO3 as precipitant. The X-ray diffraction patterns of Al-rich hydrotalcite precursors showed the presence of crystalline phases of brucite and gibbsite. It was shown that chemical composition, texture, acid-base properties of the active sites and also Mg/Al ratio strongly affect the formation of the products in the oxidation of isopropanol. The Al-rich catalysts were much more active than the Mg-rich ones, converting isopropanol mainly to propylene.

Contaminação provocada por um depósito de lixo no aqüífero Alter do Chão em Manaus - AM

Este trabalho discute a composição química da água do aqüífero Alter do Chão na área do entorno de um lixão na cidade de Manaus. Foram analisados pH, Eh, turbidez, nitrato, nitrito, amônia e os elementos Cl, F, Si, K, Na, Ca, Mg, Al, As, Mn, P, Sb, Ba, Cr, Fe, Se, Sn, Cd, Cu, Pb e Zn, em dois períodos, no final do período chuvoso e na estiagem, em 18 poços e cacimbas. De acordo com os resultados obtidos, a água está comprometida para consumo humano na quase totalidade dos poços amostrados, em conseqüência dos elevados teores de Al, Fe, As, Cd, Pb, Sb e Se, dos compostos nitrogenados e também por contaminações pontuais de Mn e Zn. A pluma de contaminação, que se expande no final do período chuvoso, estende-se para leste e sudeste do lixão, em função das direções naturais de fluxo do aqüífero e do baixo potenciométrico gerado pelo igarapé que corta a área.

Alterações dos nutrientes no solo e nas plantas em consórcio de eucalipto e acácia negra

O consórcio de eucalipto e acácia negra pode trazer benefícios ecológicos e econômicos, tendo em vista a diversidade ambiental e redução dos custos com adubação nitrogenada. Este trabalho teve o objetivo de quantificar os nutrientes no solo e nas plantas e avaliar o crescimento e a produção de eucalipto em consórcio com acácia negra. Foram estudados sistemas de cultivo simples e consorciado de Eucalyptus saligna (Smith) e Acacia mearnsii (De Wild.), com 45 meses de idade, em Argissolo Vermelho-Amarelo, no estado do Rio Grande do Sul. O espaçamento foi de 4,0 x 1,5 m e, no consórcio, as espécies foram plantadas em fileiras alternadas. Quantificaram-se N total, P, K, Ca, Mg, Al e matéria orgânica no solo e N total, P, K, Ca e Mg nas plantas. Avaliaram-se altura e diâmetro das árvores, bem como o volume de madeira produzido. As amostras de solo foram coletadas nas profundidades de 0-5, 5-10, 10-20 e 20-40 cm. Os resultados demonstraram maior teor de matéria orgânica e nitrogênio total no solo do consórcio em relação ao eucalipto simples. Solo sob cultivo simples de acácia mostrou maior teor de K, Ca e Mg que nos povoamentos em que o eucalipto estava presente. Plantas de eucalipto consorciado absorveram mais nitrogênio (22%) do que as do cultivo simples. O volume total de madeira no consórcio não diferiu do cultivo simples de eucalipto, embora o eucalipto tenha contribuído com 64% da produção do consórcio. O consórcio beneficiou a nutrição de nitrogênio do eucalipto e aumentou o estoque de nitrogênio no ecossistema, enquanto manteve a produção total de madeira.

Alterações nas propriedades químicas e físicas de um chernossolo com diferentes coberturas vegetais

O agrossistema de Itapetinga, Bahia, tem a pecuária como uma das principais atividades econômicas. Sabe-se que a pecuária é uma atividade que causa impactos diretos no solo, no subsolo e na vegetação. Este estudo teve o objetivo de verificar mudanças nas características químicas e texturais de um solo com diferentes coberturas vegetais na região pastoril de Itapetinga, por meio de amostragens realizadas numa seqüência floresta-capoeira-pasto. As amostras foram coletadas ao longo de uma transecção, com 36 pequenas trincheiras de 60 cm de profundidade, espaçadas de 5 m (12 amostras sob mata, 12 sob capoeira e 12 sob pasto), em três profundidades: 0-10, 10-20 e 20-40 cm. Cada três pontos de coleta, ao longo da transecção, foram tomados como uma amostra composta. Os resultados foram submetidos à análise de variância, e a comparação das médias foi feita pelo teste de Tukey a 5 %. Observaram-se diferenças nas propriedades químicas e na matéria orgânica dos solos estudados. Mudanças na cobertura vegetal original, no sentido floresta - pastagem, foram acompanhadas por uma diminuição nos teores de P, K, Ca, Mg, Al, H, soma de bases, saturação por bases e capacidade de troca catiônica, indicando que, de maneira geral, estas propriedades foram alteradas pela introdução e uso de pastagens. Observou-se, também, diferença significativa na textura do solo com relação ao tipo de vegetação, sendo observados maiores teores de argila na mata, capoeira e pasto, seqüencialmente, e maiores teores de areia no pasto.

Protective effect of divalent cations against aluminum toxicity in soybean

A large proportion of soybean fields in Brazil are currently cultivated in the Cerrado region, where the area planted with this crop is growing considerably every year. Soybean cultivation in acid soils is also increasing worldwide. Since the levels of toxic aluminum (Al) in these acid soils is usually high it is important to understand how cations can reduce Al rhizotoxicity in soybean. In the present study we evaluated the ameliorative effect of nine divalent cations (Ca, Mg, Mn, Sr, Sn, Cu, Zn, Co and Ba) in solution culture on Al rhizotoxicity in soybean. The growth benefit of Ca and Mg to plants in an acid Inceptisol was also evaluated. In this experiment soil exchangeable Ca:Mg ratios were adjusted to reach 10 and 60 % base saturation, controlled by different amounts of CaCl2 or MgCl2 (at proportions from 100:0 up to 0:100), without altering the soil pH level. The low (10 %) and adequate (60 %) base saturation were used to examine how plant roots respond to Al at distinct (Ca + Mg)/Al ratios, as if they were growing in soils with distinct acidity levels. Negative and positive control treatments consisted of absence (under native soil or undisturbed conditions) or presence of lime (CaCO3) to reach 10 and 60 % base saturation, respectively. It was observed that in the absence of Aluminum, Cu, Zn, Co and Sn were toxic even at a low concentration (25 µmol L-1), while the effect of Mn, Ba, Sr and Mg was positive or absent on soybean root elongation when used in concentrations up to 100 µmol L-1. At a level of 10 µmol L-1 Al, root growth was only reverted to the level of control plants by the Mg treatment. Higher Tin doses led to a small alleviation of Al rhizotoxicity, while the other cations reduced root growth or had no effect. This is an indication that the Mg effect is ion-specific and not associated to an electrostatic protection mechanism only, since all ions were divalent and used at low concentrations. An increased exchangeable Ca:Mg ratio (at constant soil pH) in the acid soil almost doubled the soybean shoot and root dry matter even though treatments did not modify soil pH and exchangeable Al3+. This indicates a more efficient alleviation of Al toxicity by Mg2+ than by Ca2+. The reason for the positive response to Mg2+ was not the supply of a deficient nutrient because CaCO3 increased soybean growth by increasing soil pH without inducing Mg2+ deficiency. Both in hydroponics and acid soil, the reduction in Al toxicity was accompanied by a lower Al accumulation in plant tissue, suggesting a competitive cation absorption and/or exclusion of Al from plant tissue stimulated by an Mg-induced physiological mechanism.

Bacteria diversity and microbial biomass in forest, pasture and fallow soils in the southwestern Amazon basin

It is well-known that Amazon tropical forest soils contain high microbial biodiversity. However, anthropogenic actions of slash and burn, mainly for pasture establishment, induce profound changes in the well-balanced biogeochemical cycles. After a few years the grass yield usually declines, the pasture is abandoned and is transformed into a secondary vegetation called "capoeira" or fallow. The aim of this study was to examine how the clearing of Amazon rainforest for pasture affects: (1) the diversity of the Bacteria domain evaluated by Polymerase Chain Reaction and Denaturing Gradient Gel Electrophoresis (PCR-DGGE), (2) microbial biomass and some soil chemical properties (pH, moisture, P, K, Ca, Mg, Al, H + Al, and BS), and (3) the influence of environmental variables on the genetic structure of bacterial community. In the pasture soil, total carbon (C) was between 30 to 42 % higher than in the fallow, and almost 47 % higher than in the forest soil over a year. The same pattern was observed for N. Microbial biomass in the pasture was about 38 and 26 % higher than at fallow and forest sites, respectively, in the rainy season. DGGE profiling revealed a lower number of bands per area in the dry season, but differences in the structure of bacterial communities among sites were better defined than in the wet season. The bacterial DNA fingerprints in the forest were stronger related to Al content and the Cmic:Ctot and Nmic:Ntot ratios. For pasture and fallow sites, the structure of the Bacteria domain was more associated with pH, sum of bases, moisture, total C and N and the microbial biomass. In general microbial biomass in the soils was influenced by total C and N, which were associated with the Bacteria domain, since the bacterial community is a component and active fraction of the microbial biomass. Results show that the genetic composition of bacterial communities in Amazonian soils changed along the sequence forest-pasture-fallow.

Relationships between microbial activity and soil physical and chemical properties in native and reforested Araucaria angustifolia forests in the state of São Paulo, Brazil

Araucaria angustifolia (Bert.) O. Kuntze is the main component of the Mixed Ombrophilous forest and, in the State of São Paulo, it is associated with a high diversity of soil organisms, essential for the maintenance of soil quality, making the conservation of this ecosystem a major and pressing challenge. The objective of this study was to identify the physical and chemical properties that are most closely correlated with dehydrogenase enzyme activity, basal respiration and microbial biomass under native (NF) and replanted (RF) Araucaria angustifolia forests in three regions of the state of São Paulo, in winter and summer. The main differentiating factors between the areas were also determined. Each forest was represented by three true replications; at each site, from around the araucaria trees, 15 soil samples (0-20 cm) were collected to evaluate the soil physical, chemical and microbiological properties. At the same points, forest litter was sampled to assess mass and chemical properties. The following microbiological properties were evaluated: microbial biomass carbon (MBC), basal respiration (CO2-C), metabolic quotient (Q: CO2), dehydrogenase enzyme activity (DHA) as well as the physical properties (moisture, bulk density, macroporosity and total porosity), soil chemical properties [pH, organic carbon (org-C), P, Ca, K, Mg, Al, H+Al], litter dry mass, and C, N and S contents. The data were subjected to analysis of variance (TWO-WAY: ANOVA). A Canonical Discriminant Analysis (CDA) and a Canonical Correlation Analysis (CCA) were also performed. In the soil under NF, the values of K, P, soil macroporosity, and litter dry mass were higher and Q: CO2 and DHA lower, regardless of the sampling period, and DHA was lower in winter. In the RF areas, the levels of moisture, porosity and Q: CO2 were higher in both sampling periods, and DHA was higher in winter. The MBC was only higher under NF in the summer, while the litter contents of C, N and S were greater in winter. In winter, CCA showed a high correlation of DHA with CO2-C, pH and H+Al, while in the summer org-C, moisture, Mg, pH and litter C were more associated with DHA and CO2-C. The CDA indicated H+Al, available P, total porosity, litter S content, and soil moisture as the most discriminating variables between NF and RF, but moisture was the most relevant, in both seasons and CO2-C only in winter. The combined analysis of CCA and CDA showed that the contribution of the microbiological variables to a differentiation of the areas was small at both samplings, which may indicate that the period after reforestation was long enough to allow an almost complete recovery of the microbial activity.

Uso da terra e a qualidade microbiana de agregados de um Latossolo Vermelho-Amarelo

A maioria dos estudos relacionados à agregação do solo associa o efeito de manejos ou tipos de uso da terra ao teor de matéria orgânica. No entanto, a avaliação de microrganismos e seus processos, feita diretamente em estruturas indeformadas do solo, permite maior entendimento do real efeito de diferentes tipos de manejos exercidos sobre esse. Assim, o objetivo deste trabalho foi avaliar modificações impostas por diferentes tipos de uso da terra (pastagem, mata de eucalipto, mata com araucária, plantio convencional com cenoura e plantio convencional com abóbora) em atributos químicos (pH, Ca, Mg, Al, P, K, S e matéria orgânica) e físicos (diâmetro médio geométrico - DMG, diâmetro médio ponderado - DMP, densidade do solo e densidade de partículas) e na qualidade microbiana (atividade e carbono microbianos, micélio extrarradicular total de fungos micorrízicos arbusculares e quociente metabólico - qCO2) de classes de tamanho de agregados (I- 4,00 a 2,36 mm; II- 2,36 a 1,18 mm; III- 1,18 a 0,60 mm; IV- 0,60 a 0,30 mm; e V- 0,30 a 0,15 mm) de um Latossolo Vermelho-Amarelo, no sul de Minas Gerais. Os resultados evidenciaram que os tipos de uso da terra interferem na formação, no tamanho e na qualidade microbiana dos agregados. Em agregados menores (classes IV e V), há redução de micélio extrarradicular de fungos e biomassa microbiana e aumento da atividade e do quociente metabólico, independentemente do tipo de uso da terra. A qualidade microbiana de agregados maiores do solo sob mata de araucária, com tamanho entre 0,60 e 4,00 mm (I, II e III), é semelhante a todas as classes de tamanho de agregados do solo sob mata de eucalipto, enquanto a de agregados menores de 0,60 mm (IV e V) é semelhante a todas de tamanho de agregados da pastagem. Agregados do cultivo convencional, diferentemente dos demais tipos de uso da terra, apresentam baixa qualidade microbiana e relação com a fertilidade do solo.

Using numerical classification of profiles based on Vis-NIR spectra to distinguish soils from the Piracicaba Region, Brazil

Considering that information from soil reflectance spectra is underutilized in soil classification, this paper aimed to evaluate the relationship of soil physical, chemical properties and their spectra, to identify spectral patterns for soil classes, evaluate the use of numerical classification of profiles combined with spectral data for soil classification. We studied 20 soil profiles from the municipality of Piracicaba, State of São Paulo, Brazil, which were morphologically described and classified up to the 3rd category level of the Brazilian Soil Classification System (SiBCS). Subsequently, soil samples were collected from pedogenetic horizons and subjected to soil particle size and chemical analyses. Their Vis-NIR spectra were measured, followed by principal component analysis. Pearson's linear correlation coefficients were determined among the four principal components and the following soil properties: pH, organic matter, P, K, Ca, Mg, Al, CEC, base saturation, and Al saturation. We also carried out interpretation of the first three principal components and their relationships with soil classes defined by SiBCS. In addition, numerical classification of the profiles based on the OSACA algorithm was performed using spectral data as a basis. We determined the Normalized Mutual Information (NMI) and Uncertainty Coefficient (U). These coefficients represent the similarity between the numerical classification and the soil classes from SiBCS. Pearson's correlation coefficients were significant for the principal components when compared to sand, clay, Al content and soil color. Visual analysis of the principal component scores showed differences in the spectral behavior of the soil classes, mainly among Argissolos and the others soils. The NMI and U similarity coefficients showed values of 0.74 and 0.64, respectively, suggesting good similarity between the numerical and SiBCS classes. For example, numerical classification correctly distinguished Argissolos from Latossolos and Nitossolos. However, this mathematical technique was not able to distinguish Latossolos from Nitossolos Vermelho férricos, but the Cambissolos were well differentiated from other soil classes. The numerical technique proved to be effective and applicable to the soil classification process.

GERAÇÃO DE DRENAGEM ÁCIDA E DE CONTAMINAÇÃO POR METAIS PESADOS EM PERFIS DE SOLOS CONSTRUÍDOS EM ÁREA DE MINERAÇÃO DE CARVÃO

RESUMO Os solos construídos após a extração de carvão a céu aberto são compostos do solo superficial e, ou, do estéril de mineração. As propriedades químicas desses solos diferem das propriedades dos solos naturais, principalmente em razão do processo de sulfurização. O objetivo deste trabalho foi avaliar o potencial de acidificação da pirita e de contaminação com metais pesados ao longo de perfis de solos construídos após mineração de carvão, em áreas de diferentes idades, com e sem recuperação ambiental concomitante com a lavra. Foram selecionadas áreas mineradas denominadas de I e II, sem recuperação ambiental durante a lavra e compostas somente pelo estéril de mineração, representando as áreas mais antigas, e IV e VII, contendo topsoil e em alguns locais na camada de argila, constituindo as áreas mais jovens deste estudo. Foram coletadas amostras deformadas até 2 m de profundidade. Analisaram-se granulometria, densidade de partículas, pH em água, Ca, Mg, Al, K, Na, P, H+Al, potencial de acidificação, potencial de neutralização, potencial líquido, teor de C orgânico e condutividade elétrica no extrato da pasta saturada. Também foram extraídos os metais potencialmente biodisponíveis pela metodologia USEPA 3050B, cujos resultados foram comparados com os valores orientadores de prevenção e investigação para solos. Na análise univariada, foi aplicada a estatística descritiva e o teste de aderência de Kolmogorov-Smirnov. O grau de dispersão de cada variável foi avaliado qualitativamente e classificado como: baixo, moderado ou alto. A análise multivariada de componentes principais foi realizada para os solos construídos das áreas I, II, IV e VII; posteriormente, foram construídos biplots dos primeiros componentes principais. Os solos construídos das áreas mais antigas evidenciaram menores pHs e significativo potencial de acidificação. As camadas superficiais detopsoil, dos solos das áreas IV e VII, apesar de proporcionar condições químicas favoráveis ao estabelecimento de culturas agrícolas, não evitaram a formação de drenagem ácida em profundidade. O processo de sulfurização e sua relação com a liberação de metais foi melhor caracterizado pela análise de componentes principais realizada nas áreas IV e VII, em razão da correlação entre pH e saturação por bases nos estéreis só se expressar em saturações por bases acima de 40 %, não observada nos materiais dos estéreis das áreas I e II.

Efeito da composição das correntes do conversor das unidades de FCC no desempenho catalítico de aditivos DESOx

Hydrotalcite-like compounds having Mg partially replaced by Cu or Mn were prepared and used as precursors for two mixed oxides (Cu-OM50 and Mn-OM50) that were evaluated for SOx removal in the presence of O2, NO and CO. Under SO2/O2 reaction system, SOx removal was slightly higher over Cu-OM50. The addition of CO and NO to the feed markedly hindered the SO2 oxidation over Cu-OM50 while no significant effect was observed for Mn-OM50. For the regeneration step, the use of propane instead of H2 reduces regeneration capacity, mainly for Cu-OM50. Mn-OM50 was less affected by the feed composition, suggesting that it was a promising additive for SOx removal.

Immobilization of laccase on hybrid layered double hydroxide

Crystals of Mg/Al layered double hydroxide were synthesized by alkaline precipitation and treated in an aqueous solution of glutamic acid. The glutamate ions were not intercalated into the interlayer space, but were detected in the material by Fourier transform infrared spectroscopy, suggesting that only the external surfaces of crystals were modified with glutamate ions. The resulting hybrid material was tested as a support for immobilization of the enzyme laccase (Myceliophthora thermophila). The immobilized enzyme preparation was characterized by electronic paramagnetic resonance spectroscopy and by assays of catalytic activity. The activity of the immobilized laccase was 97% of the activity in the free enzyme. Layered double hydroxide is a suitable support for use in remediation of soil studies.

Synthesis of liquid menthol by hydrogenation of dementholized peppermint oil over Ni catalysts

Hydrogenation of (-)-menthone and (+)-isomenthone was studied at 2.7 MPa and 100 ºC. The objective was to produce a liquid menthol mixture rich in (-)-menthol from dementholized peppermint oil. Ni-based catalysts were tested and compared for this reaction: a) 6 and 12% Ni dispersed into a nonstoichiometric magnesium aluminate (Ni-Mg-Al) with spinel structure; b) Ni-Raney catalyst. Both types of catalysts were active for (-)-menthone and (+)-isomenthone hydrogenation. Lower conversion but higher selectivity to (-)-menthol was obtained with Ni-Mg-Al catalysts. However, they rapidly lost their activity. Instead Ni-Raney catalysts kept its original activity even after several hydrogenation runs.

Hidróxidos duplos lamelares à base de escória de alto forno

Hydrotalcite like compounds (HT) were prepared by co-precipitation (Mg/Al = 3.5), using an acid solution with blast furnace slag and MgCl2.6H2O and aqueous solutions of NaOH. The following synthesis variables were investigated: temperature (30 and 45 ºC) and pH (9 and 12). Depending of the temperature two systems were observed: Mg-Al-CO3 (T = 30 ºC); Mg-Al-Cl-CO3 (T = 45 ºC). An increase in the pH of synthesis and Mg2+ concentration produced HTs well-crystallized and with greater values of all cell parameters. The study showed the potentiality of BFS in the synthesis of well-crystallized LDHs without the presence of other crystalline phases.