Use of solvent extraction to remediate soils contaminated with hydrocarbons

The main objective of this research is to exploit the possibility of using an ex situ solvent extraction technique for the remediation of soils contaminated with semi-volatile petroleum hydrocarbons. The composition of the organic phase was chosen in order to form a single phase mixture with an aqueous phase and simultaneously not being disturbed (forming stable emulsions) by the soil particles hauling the contaminants. It should also permit a regeneration of the organic solvent phase. As first, we studied the miscibility domain of the chosen ternary systems constituted by ethyl acetate–acetone–water. This system proved to satisfy the previous requirements allowing for the formation of a single liquid phase mixture within a large spectrum of compositions, and also allowing for an intimate contact with the soil. Contaminants in the diesel range within different functional groups were selected: xylene, naphthalene and hexadecane. The analytical control was done by gas chromatography with FID detector. The kinetics of the extractions proved to be fast, leading to equilibrium after 10 min. The effect of the solid–liquid ratio on the extraction efficiency was studied. Lower S/L ratios (1:8, w/v) proved to be more efficient, reaching recoveries in the order of 95%. The option of extraction in multiple contacts did not improve the recovery in relation to a single contact. The solvent can be regenerated by distillation with a loss around 10%. The contaminants are not evaporated and they remain in the non-volatile phase. The global results show that the ex situ solvent extraction is technically a feasible option for the remediation of semi-volatile aromatic, polyaromatic and linear hydrocarbons.

Interlimb relation during the double support phase of gait: an electromyographic, mechanical and energy based analysis

The purpose of this study is to analyse the interlimb relation and the influence of mechanical energy on metabolic energy expenditure during gait. In total, 22 subjects were monitored as to electromyographic activity, ground reaction forces and VO2 consumption (metabolic power) during gait. The results demonstrate a moderate negative correlation between the activity of tibialis anterior, biceps femoris and vastus medialis of the trailing limb during the transition between midstance and double support and that of the leading limb during double support for the same muscles, and between these and gastrocnemius medialis and soleus of the trailing limb during double support. Trailing limb soleus during the transition between mid-stance and double support was positively correlated to leading limb tibialis anterior, vastus medialis and biceps femoris during double support. Also, the trailing limb centre of mass mechanical work was strongly influenced by the leading limbs, although only the mechanical power related to forward progression of both limbs was correlated to metabolic power. These findings demonstrate a consistent interlimb relation in terms of electromyographic activity and centre of mass mechanical work, being the relations occurred in the plane of forward progression the more important to gait energy expenditure.

Interlimb coordination during the stance phase of gait in subjects with stroke

Objective: To analyze the relation between contralesional and ipsilesional limbs in subjects with stroke during step-to-step transition of walking. Design: Observational, transversal, analytical study with a convenience sample. Setting: Physical medicine and rehabilitation clinic. Participants: Subjects (nZ16) with poststroke hemiparesis with the ability to walk independently and healthy controls (nZ22). Interventions: Not applicable. Main Outcome Measures: Bilateral lower limbs electromyographic activity of the soleus (SOL), gastrocnemius medialis, tibialis anterior, biceps femoris, rectus femoris, and vastus medialis (VM) muscles and the ground reaction force were analyzed during double-support and terminal stance phases of gait. Results: The propulsive impulse of the contralesional trailing limb was negatively correlated with the braking impulse of the leading limb during double support (rZ .639, PZ.01). A moderate functional relation was observed between thigh muscles (rZ .529, PZ.035), and a strong and moderate dysfunctional relation was found between the plantar flexors of the ipsilesional limb and the vastus medialis of the contralesional limb, respectively (SOL-VM, rZ .80, P<.001; gastrocnemius medialis-VM, rZ .655, PZ.002). Also, a functional moderate negative correlation was found between the SOL and rectus femoris muscles of the ipsilesional limb during terminal stance and between the SOL (rZ .506, PZ.046) and VM (rZ .518, PZ.04) muscles of the contralesional limb during loading response, respectively. The trailing limb relative impulse contribution of the contralesional limb was lower than the ipsilesional limb of subjects with stroke (PZ.02) and lower than the relative impulse contribution of the healthy limb (PZ.008) during double support. Conclusions: The findings obtained suggest that the lower performance of the contralesional limb in forward propulsion during gait is related not only to contralateral supraspinal damage but also to a dysfunctional influence of the ipsilesional limb.

Multiresidue pesticides analysis in soils using modified QuEChERS with disposable pipette extraction and dispersive solid-phase extraction

QuEChERS original method was modified into a new version for pesticides determination in soils. The QuEChERS method is based on liquid–liquid portioning with ACN and was followed by cleanup step using dispersive SPE and disposable pipette tips. Gas chromatographic separation with MS detection was carried out for pesticides quantification. The method was validated using recovery experiments for 36 multiclass pesticides. Mean recoveries of pesticides at each of the four spiking levels between 10–300 µg/kg of soil ranged from 70–120% for 26 pesticides with RSD values less than 15%. The method achieved low limit of detection less than 7.6 µ g/kg. Matrix effects were observed for 13 pesticides. Matrix effects were compensated by using matrix-matched calibration. The method was applied successfully using d-SPE or DPX in the analysis of the pesticides in soils from organic farming and integrated pest management.

CuxSnSx+1 (x = 2, 3) thin films grown by sulfurization of metallic precursors deposited by dc magnetron sputtering

We report the results of the growth of Cu-Sn-S ternary chalcogenide compounds by sulfurization of dc magnetron sputtered metallic precursors. Tetragonal Cu2SnS3 forms for a maximum sulfurization temperature of 350 ºC. Cubic Cu2SnS3 is obtained at sulfurization temperatures above 400 ºC. These results are supported by XRD analysis and Raman spectroscopy measurements. The latter analysis shows peaks at 336 cm-1, 351 cm-1 for tetragonal Cu2SnS3, and 303 cm-1, 355 cm-1 for cubic Cu2SnS3. Optical analysis shows that this phase change lowers the band gap from 1.35 eV to 0.98 eV. At higher sulfurization temperatures increased loss of Sn is expected in the sulphide form. As a consequence, higher Cu content ternary compounds like Cu3SnS4 grow. In these conditions, XRD and Raman analysis only detected orthorhombic (Pmn21) phase (petrukite). This compound has Raman peaks at 318 cm-1, 348 cm-1 and 295 cm-1. For a sulfurization temperature of 450 ºC the samples present a multi-phase structure mainly composed by cubic Cu2SnS3 and orthorhombic (Pmn21) Cu3SnS4. For higher temperatures, the samples are single phase and constituted by orthorhombic (Pmn21) Cu3SnS4. Transmittance and reflectance measurements were used to estimate a band gap of 1.60 eV. For comparison we also include the results for Cu2ZnSnS4 obtained using similar growth conditions.

Two-type heterogeneous multiprocessor scheduling: Is there a phase transition? (Extended Abstract)

Consider the problem of non-migratively scheduling a set of implicit-deadline sporadic tasks to meet all deadlines on a two-type heterogeneous multiprocessor platform. We ask the following question: Does there exist a phase transition behavior for the two-type heterogeneous multiprocessor scheduling problem? We also provide some initial observations via simulations performed on randomly generated task sets.

A pseudo-medium-wide 8-competitive interface for two-level compositional real-time scheduling of constrained- deadline sporadic tasks on a uniprocessor

Compositional real-time scheduling clearly requires that ”normal” real-time scheduling challenges are addressed but challenges intrinsic to compositionality must be addressed as well, in particular: (i) how should interfaces be described? and (ii) how should numerical values be assigned to parameters constituting the interfaces? The real-time systems community has traditionally used narrow interfaces for describing a component (for example, a utilization/bandwidthlike metric and the distribution of this bandwidth in time). In this paper, we introduce the concept of competitive ratio of an interface and show that typical narrow interfaces cause poor performance for scheduling constrained-deadline sporadic tasks (competitive ratio is infinite). Therefore, we explore more expressive interfaces; in particular a class called medium-wide interfaces. For this class, we propose an interface type and show how the parameters of the interface should be selected. We also prove that this interface is 8-competitive.

Modeling of the lung impedance using a fractional order ladder network with constant phase elements

The self similar branching arrangement of the airways makes the respiratory system an ideal candidate for the application of fractional calculus theory. The fractal geometry is typically characterized by a recurrent structure. This study investigates the identification of a model for the respiratory tree by means of its electrical equivalent based on intrinsic morphology. Measurements were obtained from seven volunteers, in terms of their respiratory impedance by means of its complex representation for frequencies below 5 Hz. A parametric modeling is then applied to the complex valued data points. Since at low-frequency range the inertance is negligible, each airway branch is modeled by using gamma cell resistance and capacitance, the latter having a fractional-order constant phase element (CPE), which is identified from measurements. In addition, the complex impedance is also approximated by means of a model consisting of a lumped series resistance and a lumped fractional-order capacitance. The results reveal that both models characterize the data well, whereas the averaged CPE values are supraunitary and subunitary for the ladder network and the lumped model, respectively.

Experimental backlash study in mechanical manipulators

The behavior of mechanical manipulators with backlash is analyzed. In order to acquire and study the signals an experimental setup is implemented. The signal processing capabilities of the wavelets are used for de-noising the experimental signals and the energy of the obtained components is analyzed. To evaluate the backlash effect upon the robotic system, it is proposed an index based on the pseudo phase plane representation. Several tests are developed that demonstrate the coherence of the results.

Dynamics of the Dow Jones and the NASDAQ stock indexes

The goal of this study is the analysis of the dynamical properties of financial data series from worldwide stock market indices. We analyze the Dow Jones Industrial Average ( ∧ DJI) and the NASDAQ Composite ( ∧ IXIC) indexes at a daily time horizon. The methods and algorithms that have been explored for description of physical phenomena become an effective background, and even inspiration, for very productive methods used in the analysis of economical data. We start by applying the classical concepts of signal analysis, Fourier transform, and methods of fractional calculus. In a second phase we adopt a pseudo phase plane approach.

Filtering method in backlash phenomena analysis

The behavior of robotic manipulators with backlash is analyzed. Based on the pseudo-phase plane two indices are proposed to evaluate the backlash effect upon the robotic system: the root mean square error and the fractal dimension. For the dynamical analysis the noisy signals captured from the system are filtered through wavelets. Several tests are developed that demonstrate the coherence of the results.

Otimização de uma cadeia de logística interna

Atualmente qualquer organização que se queira manter no ativo, tem que obrigatoriamente inovar, reduzir o desperdício associado ao processo produtivo e simultaneamente simplificar as tarefas diárias dos seus colaboradores. E é sobre estes princípios que este trabalho é baseado, ou seja, pretende-se através da aplicação de ferramentas Lean, a melhoria contínua do processo de produção da Schmitt Elevadores. Numa fase inicial foi necessário um estudo dos diferentes fluxos de materiais, que permitiu a conceção do VSM (Value Stream Mapping). O VSM juntamente com o diagrama de Spaghetti permitiram a identificação de algumas das fontes de desperdício, relacionadas essencialmente com o excesso de movimentações. Considerando o âmbito do estágio, logística interna, e reunidas as causas de desperdício verificadas nesta área, procedeu-se à criação de um ciclo de entrega de materiais, por parte do operador logístico, baseado no conceito de milk run. Verificaram-se também problemas ao nível da gestão de stocks, pelo que também foi necessária intervenção nesta área. A aplicação das medidas mencionadas anteriormente irá traduzir-se em ganhos para o processo produtivo, nomeadamente, na criação de rotinas para os operadores logísticos; evitar deslocações por parte dos operadores de cada processo e manter em supermercado a quantidade suficiente de cada artigo, para fazer face à variabilidade da procura.

Plataforma web de informação automobilística

Esta dissertação enquadra-se no âmbito dos Sistemas de Informação, em concreto, no desenvolvimento de aplicações Web, como é o caso de um website. Com a utilização em larga escala dos meios tecnológicos tem-se verificado um crescimento exponencial dos mesmos, o que se traduz na facilidade com que podem ser encontradas na Internet diversos tipos de plataformas informáticas. Além disso, hoje em dia, uma grande parte das organizações possui o seu próprio sítio na Internet, onde procede à divulgação dos seus serviços e/ou produtos. Pretende-se com esta dissertação explorar estas novas tecnologias, nomeadamente, os diagramas UML - Unified Modeling Language e a concepção de bases de dados, e posteriormente desenvolver um website. Com o desenvolvimento deste website não se propõe a criação de uma nova tecnologia, mas o uso de diversas tecnologias em conjunto com recurso às ferramentas UML. Este encontra-se organizado em três fases principais: análise de requisitos, implementação e desenho das interfaces. Na análise de requisitos efectuou-se o levantamento dos objectivos propostos para o sistema e das necessidades/requisitos necessários à sua implementação, auxiliado essencialmente pelo Diagrama de Use Cases do sistema. Na fase de implementação foram elaborados os arquivos e directórios que formam a arquitectura lógica de acordo com os modelos descritos no Diagrama de Classes e no Diagrama de Entidade-Relação. Os requisitos identificados foram analisados e usados na composição das interfaces e sistema de navegação. Por fim, na fase de desenho das interfaces foram aperfeiçoadas as interfaces desenvolvidas, com base no conceito artístico e criativo do autor. Este aperfeiçoamento vai de encontro ao gosto pessoal e tem como objectivo elaborar uma interface que possa também agradar ao maior número possível de utilizadores. Este pode ser observado na maneira como se encontram distribuídas as ligações (links) entre páginas, nos títulos, nos cabeçalhos, nas cores e animações e no seu design em geral. Para o desenvolvimento do website foram utilizadas diferentes linguagens de programação, nomeadamente a HyperText Markup Language (HTML), a Page Hypertext Preprocessor (PHP) e Javascript. A HTML foi utilizada para a disposição de todo o conteúdo visível das páginas e para definição do layout das mesmas e a PHP para executar pequenos scripts que permitem interagir com as diferentes funcionalidades do site. A linguagem Javascript foi usada para definir o design das páginas e incluir alguns efeitos visuais nas mesmas. Para a construção das páginas que compõem o website foi utilizado o software Macromedia Dreamweaver, o que simplificou a sua implementação pela facilidade com que estas podem ser construídas. Para interacção com o sistema de gestão da base de dados, o MySQL, foi utilizada a aplicação phpMyAdmin, que simplifica o acesso à base de dados, permitindo definir, manipular e consultar os seus dados.

Siderophore Production by Bacillus megaterium: Effect of Growth Phase and Cultural Conditions

Siderophore production by Bacillus megaterium was detected, in an iron-deficient culture medium, during the exponential growth phase, prior to the sporulation, in the presence of glucose; these results suggested that the onset of siderophore production did not require glucose depletion and was not related with the sporulation. The siderophore production by B. megaterium was affected by the carbon source used. The growth on glycerol promoted the very high siderophore production (1,182 μmol g−1 dry weight biomass); the opposite effect was observed in the presence of mannose (251 μmol g−1 dry weight biomass). The growth in the presence of fructose, galactose, glucose, lactose, maltose or sucrose, originated similar concentrations of siderophore (546–842 μmol g−1 dry weight biomass). Aeration had a positive effect on the production of siderophore. Incubation of B. megaterium under static conditions delayed and reduced the growth and the production of siderophore, compared with the incubation in stirred conditions.

Comparison of Disposable Pipette Extraction and Dispersive Solid-Phase Extraction in the QuEChERS Method for Analysis of Pesticides in Strawberries

In this study, we sought to assess the applicability of GC–MS/MS for the identification and quantification of 36 pesticides in strawberry from integrated pest management (IPM) and organic farming (OF). Citrate versions of QuEChERS (quick, easy, cheap, effective, rugged and safe) using dispersive solid-phase extraction (d-SPE) and disposable pipette extraction (DPX) for cleanup were compared for pesticide extraction. For cleanup, a combination of MgSO4, primary secondary amine and C18 was used for both the versions. Significant differences were observed in recovery results between the two sample preparation versions (DPX and d-SPE). Overall, 86% of the pesticides achieved recoveries (three spiking levels 10, 50 and 200 µg/kg) in the range of 70–120%, with <13% RSD. The matrix effects were also evaluated in both the versions and in strawberries from different crop types. Although not evidencing significant differences between the two methodologies were observed, however, the DPX cleanup proved to be a faster technique and easy to execute. The results indicate that QuEChERS with d-SPE and DPX and GC–MS/MS analysis achieved reliable quantification and identification of 36 pesticide residues in strawberries from OF and IPM.