Distribution and mobility of trace elements in soils and vegetation around the mining and smelting areas of Tharsis, Riotinto and Huelva, Iberian Pyrite Belt, SW Spain

Trace elements may present an environmental hazard in the vicinity of mining and smelting activities. However, the factors controlling their distribution and transfer within the soil and vegetation systems are not always well defined. Total concentrations of up to 15,195 mg center dot kg (-1) As, 6,690 mg center dot kg(-1) Cu, 24,820 mg center dot kg(-1) Pb and 9,810 mg center dot kg(-1) Zn in soils, and 62 mg center dot kg(-1) As, 1,765 mg center dot kg(-1) Cu, 280 mg center dot kg(-1) Pb and 3,460 mg center dot kg (-1) Zn in vegetation were measured. However, unusually for smelters and mines of a similar size, the elevated trace element concentrations in soils were found to be restricted to the immediate vicinity of the mines and smelters (maximum 2-3 km). Parent material, prevailing wind direction, and soil physical and chemical characteristics were found to correlate poorly with the restricted trace element distributions in soils. Hypotheses are given for this unusual distribution: (1) the contaminated soils were removed by erosion or (2) mines and smelters released large heavy particles that could not have been transported long distances. Analyses of the accumulation of trace elements in vegetation (median ratios: As 0.06, Cu 0.19, Pb 0.54 and Zn 1.07) and the percentage of total trace elements being DTPA extractable in soils (median percentages: As 0.06%, Cu 15%, Pb 7% and Zn 4%) indicated higher relative trace element mobility in soils with low total concentrations than in soils with elevated concentrations.

Chemical characterisation of wild populations of Thymus from different climatic regions in southeast Spain

Thymus is taxonomically a very complex genus with a high frequency of hybridisation and introgression among sympatric species. The variation in accumulation of leaf-surface flavonoids was investigated in 71 wild populations of Thymus front different putative hybrid swarm areas in Andalucia, Spain. Twenty-two flavones, five flavanones, two dihydroflavonols, a flavonol and two unknowns were detected by HPLC-DAD combined with LC-APCI-MS analysis. The majority of compounds were flavones with a lutelin-type substitution of the B-ring, in contrast to previous reports on Macedonian taxa, which predominantly accumulate flavones with apigenin-type substitution of the B-ring. Anatomical and morphometric studies, supported by cluster analysis, identified pure Thymus hyemalis and Thymus baeticus populations, and a large number of putative hybrids. Flavonoid variation was closely related to morphological variation in all populations and is suspected to be a result of genetic polymorphism. Principal component analysis identified the presence of species-specific and geographically linked chemotypes and putative hybrids with mixed morphological and chemical characteristics. Qualitative and quantitative flavonoid accumulation appears to be genetically regulated, while external factors play a secondary role. Flavonoid profiles can thus provide diagnostic markers for the taxonomy of Thymus and are also useful in detecting hybridising taxa. (C) 2007 Elsevier Ltd. All rights reserved.

Development of a method fon non-destructive testing of fruits using scanning laser vibrometry (SLV)

Quality control on fruits requires reliable methods, able to assess with reasonable accuracy and possibly in a non-destructive way their physical and chemical characteristics. More specifically, a decreased firmness indicates the presence of damage or defects in the fruit or else that the fruit has exceeded its “best before date”, becoming unsuitable for consumption. In high-value exotic fruits, such as mangoes, where firmness cannot be easily measured from a simple observation of texture, colour changes and unevenness of fruits surface, the use of non-destructive techniques is highly recommendable. In particular, the application of Laser vibrometry, based on the Doppler effect, a non-contact technique sensitive to differences in displacements inferior to the nanometre, appears ideal for a possible on-line control on food. Previous results indicated that a phase shift can be in a repeatable way associated with the presence of damage on the fruit, whilst a decreased firmness results in significant differences in the displacement of the fruits under the same excitation signal. In this work, frequency ranges for quality control via the application of a sound chirp are suggested, based on the measurement of the signal coherence. The variations of the average vibration spectrum of a grid of points, or of point-by-point signal velocity allows the go-no go recognition of “firm” and “over-ripe” fruits, with notable success in the particular case of mangoes. The future exploitation of this work will include the application of this method to allow on-line control during conveyor belt distribution of fruits.

Highly resolved observations of trace gases in the lowermost stratosphere and upper troposphere from the SPURT project: an overview

During SPURT (Spurenstofftransport in der Tropopausenregion, trace gas transport in the tropopause region) we performed measurements of a wide range of trace gases with different lifetimes and sink/source characteristics in the northern hemispheric upper troposphere (UT) and lowermost stratosphere (LMS). A large number of in-situ instruments were deployed on board a Learjet 35A, flying at altitudes up to 13.7 km, at times reaching to nearly 380 K potential temperature. Eight measurement campaigns (consisting of a total of 36 flights), distributed over all seasons and typically covering latitudes between 35° N and 75° N in the European longitude sector (10° W–20° E), were performed. Here we present an overview of the project, describing the instrumentation, the encountered meteorological situations during the campaigns and the data set available from SPURT. Measurements were obtained for N2O, CH4, CO, CO2, CFC12, H2, SF6, NO, NOy, O3 and H2O. We illustrate the strength of this new data set by showing mean distributions of the mixing ratios of selected trace gases, using a potential temperature-equivalent latitude coordinate system. The observations reveal that the LMS is most stratospheric in character during spring, with the highest mixing ratios of O3 and NOy and the lowest mixing ratios of N2O and SF6. The lowest mixing ratios of NOy and O3 are observed during autumn, together with the highest mixing ratios of N2O and SF6 indicating a strong tropospheric influence. For H2O, however, the maximum concentrations in the LMS are found during summer, suggesting unique (temperature- and convection-controlled) conditions for this molecule during transport across the tropopause. The SPURT data set is presently the most accurate and complete data set for many trace species in the LMS, and its main value is the simultaneous measurement of a suite of trace gases having different lifetimes and physical-chemical histories. It is thus very well suited for studies of atmospheric transport, for model validation, and for investigations of seasonal changes in the UT/LMS, as demonstrated in accompanying and elsewhere published studies.

Xyloglucan nano-aggregates: Physico-chemical characterisation in buffer solution and potential application as a carrier for camptothecin, an anti-cancer drug

In this work, native xyloglucan was extracted from Tamarindus indica seeds (XGT), and its properties in phosphate buffer solution (PBS) were evaluated in comparison with a commercial tamarind kernel powder (TKP). The physico-chemical characteristics of the polysaccharides such as molar mass, critical concentration and intrinsic viscosity were determined. Furthermore, using spectroscopic and microscopy techniques, it was observed that the XGs tested can be considered macromolecules able to aggregate as nano-entities of 60-140 nm. The XGT tended to an ordered and compact spherical conformation determined by the Huggins constant, circular dichroism, atomic force microscopy and transmission electron microscopy. After the determination of the properties in PBS the XGs, at concentrations of 25% above their critical aggregation concentration, were used to encapsulate camptothecin, an anti-cancer drug. The XGT sample showed an encapsulation efficiency of 42% and first-order drug delivery kinetics. These results demonstrated the importance of knowledge of the physico-chemical properties of polysaccharides, for example, to better conduct their biotechnological applications as drug carriers. (C) 2010 Elsevier Ltd. All rights reserved.

Chemical modification of a nanocrystalline TiO(2) film for efficient electric connection of glucose oxidase

A novel biosensor for glucose was prepared by adsorption of 1,1`-bis(4-carboxybenzyl)-4,4`-bipyridinium di-bromide compound (H(2)BpybcBr(2)) onto the surface of a nanocrystalline TiO(2) film deposited onto FTO glasses, which was used as a platform to assemble the enzyme glucose oxidase to the electrode surface. The H(2)BpybcBr(2)/TiO(2)/FTO modified electrode was characterized by scanning electron microscopy, X-ray fluorescence image, cyclic voltammograms and spectroelectrochemical measurements. The immobilization of GOD on functionalized TiO(2) film led to stable amperometric biosensing for glucose with a linear range from 153 mu mol L(-1) to 1.30 mmol L(-1) and a detection limit of 51 mu mol L(-1). The apparent Michaelis-Menten constant (K(m)) was estimated to be 3.76 mmol L(-1), which suggested a high enzyme-substrate affinity. The maximum electrode sensitivity was 1.25 mu A mmol L(-1). The study proved that the combination of viologen mediators with TiO(2) film retains the electrocatalytic activity of the enzyme, and also enhances the electron transfer process, and hence regenerating the enzyme in the reaction with glucose. (C) 2010 Elsevier Inc. All rights reserved.

Peat as a natural solid-phase for copper preconcentration and determination in a multicommuted flow system coupled to flame atomic absorption spectrometry

The physical and chemical characteristics of peat were assessed through measurement of pH, percentage of organic matter, cationic exchange capacity (CEC), elemental analysis, infrared spectroscopy and quantitative analysis of metals by ICP OES. Despite the material showed to be very acid in view of the percentage of organic matter, its CEC was significant, showing potential for retention of metal ions. This characteristic was exploited by coupling a peat mini-column to a flow system based on the multicommutation approach for the in-line copper concentration prior to flame atomic absorption spectrometric determination. Cu(II) ions were adsorbed at pH 4.5 and eluted with 0.50 mol L(-1) HNO(3). The influence of chemical and hydrodynamic parameters, such as sample pH, buffer concentration, eluent type and concentration, sample flow-rate and preconcentration time were investigated. Under the optimized conditions, a linear response was observed between 16 and 100 mu g L(-1), with a detection limit estimated as 3 mu g L(-1) at the 99.7% confidence level and an enrichment factor of 16. The relative standard deviation was estimated as 3.3% (n = 20). The mini-column was used for at least 100 sampling cycles without significant variation in the analytical response. Recoveries from copper spiked to lake water or groundwater as well as concentrates used in hemodialysis were in the 97.3-111 % range. The results obtained for copper determination in these samples agreed with those achieved by graphite furnace atomic absorption spectrometry (GFAAS) at the 95% confidence level. (C) 2009 Elsevier B.V. All rights reserved.

Beneficiamentos da cinza de casca de arroz residual com vistas à produção de cimento composto e/ou pozolânico

A cinza de casca de arroz é um resíduo agro-industrial decorrente do processo de queima da casca de arroz, sendo largamente encontrada no Rio Grande do Sul, pois, historicamente, este Estado é o maior produtor de arroz no Brasil, com cerca de 45% da produção nacional. Empregada como fonte de energia, a casca de arroz é queimada em diversas empresas; algumas, devido à sua natureza, incorporam a cinza ao produto, mas a maioria não encontra outro destino que não o descarte em forma de aterro, criando, assim, um problema ambiental de poluição do solo, do ar e de rios e córregos. No entanto, devido à presença de elevado percentual de sílica (SiO2) na sua constituição, a cinza de casca de arroz pode ter vários empregos. Na construção civil, pode ser empregada como pozolana, conforme vários estudos já vêm demonstrando. Porém, encontra restrições por motivos como sua cor escura, que confere aos cimentos, argamassas e concretos aos quais é adicionada, uma coloração também escura, e a falta de uniformidade apresentada em termos de características químicas e, principalmente, mineralógicas. A cor escura não é um problema de ordem técnica, mas estética e de aceitação no mercado. Já a composição mineralógica está associada à atividade pozolânica e a falta de uniformidade do material disponível implica na incerteza do grau de reatividade. Este trabalho teve o objetivo de verificar a viabilidade técnica do emprego de cinzas de casca de arroz residuais na confecção de cimentos Portland composto e/ou pozolânico, a partir de beneficiamentos das mesmas, que associam tratamentos físicos, químicos e/ou térmicos, os quais têm como finalidade reverter e/ou minimizar os aspectos negativos citados. Para tanto, foram empregadas três cinzas de casca de arroz, oriundas de diferentes processos de produção e com composições mineralógicas distintas. Após definidos os tratamentos a serem aplicados, através de seleção pelos critérios de cor e composição mineralógica, as cinzas tratadas foram avaliadas quanto à sua pozolanicidade, pelo Índice de Atividade Pozolânica (IAP) da NBR 5752 e também por um IAP alterado, proposto neste trabalho. A produção de cimentos com CCA beneficiada se deu a partir de um cimento base com substituição por CCA, em massa e em diferentes percentuais. Tais cimentos foram avaliados quanto à resistência à compressão, aos tempos de pega, à pozolanicidade e à expansibilidade a quente. A análise dos dados obtidos indica que os tratamentos propostos e/ou a associação deles resultam em beneficio no desempenho das cinzas, em pelo menos um dos vários aspectos considerados. A presente pesquisa permite concluir que as CCA residuais têm potencial para serem empregadas na produção de cimentos, tanto aquelas menos cristalinas, quanto as mais cristalinas. Para tanto, devem ser beneficiadas, sendo pelo menos submetidas a tratamento físico para redução de sua granulometria. Se outros objetivos forem pretendidos, como coloração clara, os tratamentos térmico ou químico podem ser empregados.

Avaliação da qualidade da água do Rio Piranhas-Açu/RN utilizando a comunidade de macroinvertebrados bentônicos

The biomonitoring technique for water quality in water bodies has been incorporated increasingly in management of the natural resources, using mainly indices of its aquatic community characteristics. In Brazil the first efforts to use this technique was restricted to the South and the Midwest region of this country. Located in the northeast region, this study was conducted at Rio Grande do Norte state and had as main objective the assessment of water quality in the Piranhas-Açu river using benthic macroinvertebrates community as biological indicators. Thus, were applied two biotic indices, the BMWP (Biological Monitoring Working Party score system) and the IBF (Family Biotic Index). According the requirements of these indices, two periods of sampling were determined as basic methodology, in dry seasons of 2006 and 2007. The sampling sites were around the municipalities of Açu, Ipanguaçu, Alto do Rodrigues and Pendências. Physical-chemical measurements; a protocol of rapid assessment of diversity of habitats, and determination of the degree of tolerance of each taxon to organic pollution were also performed. The most abundant organisms found in the river were tolerant with the prevalence of Chironomidae (Diptera) and Melanoides tuberculata. This results, together with those ones got in indices application, showed a considerable organic pollution in the four sample places and the reaches were classified as modified to impacted. According to the used indices, this study suggest that this river have significant alteration in the biotic community and water quality on the organic pollution, and this fact, occurs in the reach of the river further downstream, where were expected a good water quality. Considering these results, measures aiming the conservation of this water body are needed regarding as it is inserted into a fragile ecosystem with dry season phenomenon, and the water of this river has extremely importance for the local economy

Influência das espécies ativas na absorção de intersticiais durante a carbonitretação a plasma do TI

Physical-chemical properties of Ti are sensible to the presence of interstitial elements. In the case of thermochemical treatments plasma assisted, the influence of different active species is not still understood. In order to contribute for such knowledge, this work purposes a study of the role played by the active species atmosphere into the Ar N2 CH4 carbonitriding plasma. It was carried out a plasma diagnostic by OES (Optical Emission Spectroscopy) in the z Ar y N2 x CH4 plasma mixture, in which z, y and x indexes represent gas flow variable from 0 to 4 sccm (cm3/min). The diagnostic presents abrupt variations of emission intensities associated to the species in determined conditions. Therefore, they were selected in order to carry out the chemical treatment and then to investigate their influences. Commercial pure Ti disks were submitted to plasma carbonitriding process using pre-established conditions from the OES measurements while some parameters such as pressure and temperature were maintained constant. The concentration profiles of interstitial elements (C and N atoms) were determined by Resonant Nuclear Reaction Analysis (NRA) resulting in a depth profile plots. The reactions used were 15N(ρ,αγ)12C and 12C(α,α)12C. GIXRD (Grazing Incidence X-Ray Diffraction) analysis was used in order to identify the presence of phases on the surface. Micro-Raman spectroscopy was used in order to qualitatively study the carbon into the TiCxN1 structure. It has been verified which the density species effectively influences more the diffusion of particles into the Ti lattice and characteristics of the layer formed than the gas concentration. High intensity of N2 + (391,4 nm) and CH (387,1 nm) species promotes more diffusion of C and N. It was observed that Hα (656,3 nm) species acts like a catalyzer allowing a deeper diffusion of nitrogen and carbon into the titanium lattice.

Síntese de pigmentos cerâmicos inorgânicos nanométricos e encapsulados com estrutura core-shell pela rota dos precursores poliméricos

The present work has as objective the development of ceramic pigments based in iron oxides and cobalt through the polymeric precursor method, as well as study their characteristics and properties using methods of physical, chemical, morphological and optical characterizations.In this work was used iron nitrate, and cobalt citrate as precursor and nanometer silica as a matrix. The synthesis was based on dissolving the citric acid as complexing agent, addition of metal oxides, such as chromophores ions and polymerization with ethylene glycol. The powder obtained has undergone pre-ignition, breakdown and thermal treatments at different calcination temperatures (700 °C, 800 °C, 900 °C, 1000 °C and 1100 °C). Thermogravimetric analyzes were performed (BT) and Differential Thermal Analysis (DTA), in order to evaluate the term decomposition of samples, beyond characterization by techniques such as BET, which classified as microporous materials samples calcined at 700 ° C, 800 º C and 900 º C and non-porous when annealed at 1000 ° C and 1100 º C, X-ray diffraction (XRD), which identified the formation of two crystalline phases, the Cobalt Ferrite (CoFe2O4) and Cristobalite (SiO2), Scanning Electron Microscopy (SEM) revealed the formation of agglomerates of particles slightly rounded;and Analysis of Colorimetry, temperature of 700 °C, 800 °C and 900 °C showed a brown color and 1000 °C and 1100 °C violet

Caracterização ambiental de bancos areno-lamosos nos campos petrolíferos de Macau e Serra (RN), como subsídio às medidas mitigadoras ao processo erosivo

On Rio Grande do Norte northern coast the process of sediment transport are intensely controlled by wind and sea (waves and currents) action, causing erosion and shoreline morphological instability. Due to the importance of such coastal zone it was realized the multi-spectral mapping and physical-chemical characterization of mudflats and mangroves aiming to support the mitigating actions related to the containment of the erosive process on the oil fields of Macau and Serra installed at the study area. The multi-spectral bands of 2000 and 2008 LANDSAT 5 TM images were submitted on the several digital processing steps and RGB color compositions integrating spectral bands and Principal Components. Such processing methodology was important to the mapping of different units on surface, together with field works. It was possible to make an analogy of the spectral characteristics of wetlands with vegetations areas (mangrove), showing the possibility to make a restoration of this area, contributing with the environmental monitoring of that ecosystem. The maps of several units were integrated in GIS environment at 1:60,000 scale, including the classification of features according to the presence or absence of vegetation cover. Thus, the strategy of methodology established that there are 10.13 km2 at least of sandy-muddy and of these approximately 0.89 km2 with the possibility to be used in a reforestation of typical flora of mangrove. The physical-chemical characterization showed areas with potential to introduce local species of mangrove and they had a pH above neutral with a mean of 8.4. The characteristic particle size is sand in the fine fractions, the high levels of carbonate, organic matter and major and trace element in general are concentrated where the sediment had the less particles size, showing the high correlation that those elements have with smaller particles of sediment. The application of that methodological strategy is relevant to the better understanding of features behavior and physical-chemical data of sediment samples collected on field allow the analysis of efficiency/capability of sandy-muddy to reforestation with local mangrove species for mitigation of the erosive action and coastal processes on the areas occupied by the oil industry

Características fisico-químicas e sensoriais da carne de bubalinos Murrah abatidos em diferentes períodos de confinamento

Objetivou-se avaliar as características físicas, químicas e sensoriais da carne de búfalos abatidos em diferentes períodos de confinamento. Foram utilizados 20 bubalinos da raça Murrah, castrados, descornados, com idade média inicial de 15 meses, abatidos aos 75, 100, 125 ou 150 dias de confinamento. Após o abate, as carcaças foram identificadas e resfriadas por 24 horas. Durante a desossa, foram colhidas amostras do contrafilé entre a 10ª e 11ª costelas para análise das características sensoriais e das perdas por cocção; entre a 11ª e 12ª costelas para avaliação da composição centesimal, do valor calórico, do pH e do índice de fragmentação miofibrilar (IFM); e entre a 12ª e 13ª costelas para a avaliação do escore de marmorização e da força de cisalhamento. A composição centesimal, o pH, a força de cisalhamento, o valor calórico, as perdas por cocção e o IFM não diferiram estatisticamente entre os períodos de confinamento. O grau de marmorização diferiu entre as idades de abate, uma vez os animais abatidos aos 75 dias de confinamento apresentaram escore de 1,25; os abatidos aos 100 e 125 dias, escore 2; e aqueles abatidos aos 150 dias de confinamento, escore 2,2. em todos os períodos de confinamento, a carne bubalina foi classificada como macia (média 3,94 kgf) e apresentou com características que não diferiram pelo painel sensorial entre os 75 e 150 dias de confinamento. O abate de bubalinos aos 75 e 150 dias de confinamento não influencia as características sensoriais sabor, aroma e cor da carne bubalina.

Termoterapia de banana 'Prata-Anã' no controle de podridões em pós-colheita

O objetivo desse estudo foi determinar a tolerância de banana (Musa spp.) 'Prata-Anã' (AAB) e do fungo Colletotrichum musae à termoterapia no controle de podridões em pós-colheita. Experimentos in vivo e in vitro foram instalados em delineamento inteiramente casualizado, seguindo um esquema fatorial 4x5 (temperatura x tempo). Os tratamentos consistiram na imersão dos frutos (buquês) e do fungo (esporos e micélio) em água aquecida a 47, 50, 53 e 56 ºC, durante 0, 3, 6, 9 e 12 min. A exposição dos frutos a 56 ºC durante 9 min causou escurecimento da casca nas extremidades dos frutos, porém, as características físicas e químicas dos frutos não foram alteradas pelos tratamentos. Frutos inoculados e tratados a 56 ºC durante 6 min não apresentaram podridões nem escurecimento da casca, enquanto aqueles não tratados apresentaram 64% da área lesionada / fruto. A partir das combinações 53 ºC / 9 mi. e 56 ºC / 3 min a germinação de esporos foi reduzida para 4% e 0%, respectivamente. A combinação 56 ºC / 12 min reduziu, mas não paralisou o crescimento micelial. O tratamento 56 ºC / 6 min retardou mas não paralisou o crescimento micelial in vitro, porém foi efetivo no controle completo das podridões in vivo. Esse tratamento evitou a manifestação de podridões no inverno (maio), mas não no verão (novembro), mostrando-se influenciado pelas condições climáticas próximas à colheita dos cachos. A termoterapia pode ser recomendada para controle de podridão em pós-colheita de banana devendo ser ajustada para diferentes estações do ano.

Impact of maintenance of Macrobrachium rosenbergii de Man, 1879 (Crustacea, Decapoda, Palaemonidae) broodstock on the water used in culture ponds

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)