Determinação turbidimétrica de dipirona em fluxo utilizando um reator contendo cloreto de prata imobilizado em resina poliéster

A simple flow injection procedure was developed for determining dipyrone (1-phenyl-2,3-dimethyl-4-methylaminomethano-5-pyrazolone sodium, metamizol, analgin) in pharmaceutical formulations. The determination is based on the reduction of Ag+ ions to Ag0 by dipyrone. A colloidal suspension of Ag0 produced was transported by carrier solution (0.01 mol L-1 NaOH) and turbidimetrically detected at 425 nm. The analytical curve for dipyrone was linear in the range from 5.0 x 10-4 to 2.5 x 10-3 mol L-1 with a correlation coefficient of 0.9990. The detection limit was 1.3 x 10-4 mol L-1 (3sigmaB/slope). The relative standard deviation for ten successive measurements was 1.8% and an analytical frequency of 45 h-1 was obtained. The recovery values from three samples ranged from 96.0 to 102%.

Análise de fármacos em material biológico: acoplamento microextração em fase sólida "no tubo" e cromatografia líquida de alta eficiência

A new solid phase microextraction (SPME) system, known as in-tube SPME, was recently developed using an open tubular fused-silica capilary column, instead of an SPME fiber, as the SPME device. On-line in-tube SPME is usually used in combination with high performance liquid chromatography. Drugs in biological samples are directly extracted and concentrated in the stationary phase of capillary columns by repeated draw/eject cycles of sample solution, and then directly transferred to the liquid chromatographic column. In-tube SPME is suitable for automation. Automated sample handling procedures not only shorten the total analysis time, but also usually provide better accuracy and precision relative to manual techniques. In-tube SPME has been demonstrated to be a very effective and highly sensitive technique to determine drugs in biological samples for various purposes such as therapeutic drug monitoring, clinical toxicology, bioavailability and pharmacokinetics.

Active sulphide mine tailings impoundments as sources of contaminated drainage: controlling factors, methods of characterisation and geochemical constraints for mitigation

Low quality mine drainage from tailings facilities persists as one of the most significant global environmental concerns related to sulphide mining. Due to the large variation in geological and environmental conditions at mine sites, universal approaches to the management of mine drainage are not always applicable. Instead, site-specific knowledge of the geochemical behaviour of waste materials is required for the design and closure of the facilities. In this thesis, tailings-derived water contamination and factors causing the pollution were investigated in two coeval active sulphide mine sites in Finland: the Hitura Ni mine and the Luikonlahti Cu-Zn-Co-Ni mine and talc processing plant. A hydrogeochemical study was performed to characterise the tailingsderived water pollution at Hitura. Geochemical changes in the Hitura tailings were evaluated with a detailed mineralogical and geochemical investigation (solid-phase speciation, acid mine drainage potential, pore water chemistry) and using a spatial assessment to identify the mechanisms of water contamination. A similar spatial investigation, applying selective extractions, was carried out in the Luikonlahti tailings area for comparative purposes (Hitura low-sulphide tailings vs. Luikonlahti sulphide-rich tailings). At both sites, hydrogeochemistry of tailings seepage waters was further characterised to examine the net results of the processes observed within the impoundments and to identify constraints for water treatment. At Luikonlahti, annual and seasonal variation in effluent quality was evaluated based on a four-year monitoring period. Observations pertinent to future assessment and mine drainage prevention from existing and future tailings facilities were presented based on the results. A combination of hydrogeochemical approaches provided a means to delineate the tailings-derived neutral mine drainage at Hitura. Tailings effluents with elevated Ni, SO₄ ^2- and Fe content had dispersed to the surrounding aquifer through a levelled-out esker and underneath the seepage collection ditches. In future mines, this could be avoided with additional basal liners in tailings impoundments where the permeability of the underlying Quaternary deposits is inadequate, and with sufficiently deep ditches. Based on the studies, extensive sulphide oxidation with subsequent metal release may already initiate during active tailings disposal. The intensity and onset of oxidation depended on e.g. the Fe sulphide content of the tailings, water saturation level, and time of exposure of fresh sulphide grains. Continuous disposal decreased sulphide weathering in the surface of low-sulphide tailings, but oxidation initiated if they were left uncovered after disposal ceased. In the sulphide-rich tailings, delayed burial of the unsaturated tailings had resulted in thick oxidized layers, despite the continuous operation. Sulphide weathering and contaminant release occurred also in the border zones. Based on the results, the prevention of sulphide oxidation should already be considered in the planning of tailings disposal, taking into account the border zones. Moreover, even lowsulphide tailings should be covered without delay after active disposal ceases. The quality of tailings effluents showed wide variation within a single impoundment and between the two different types of tailings facilities assessed. The affecting factors included source materials, the intensity of weathering of tailings and embankment materials along the seepage flow path, inputs from the process waters, the water retention time in tailings, and climatic seasonality. In addition, modifications to the tailings impoundment may markedly change the effluent quality. The wide variation in the tailings effluent quality poses challenges for treatment design. The final decision on water management requires quantification of the spatial and seasonal fluctuation at the site, taking into account changes resulting from the eventual closure of the impoundment. Overall, comprehensive hydrogeochemical mapping was deemed essential in the identification of critical contaminants and their sources at mine sites. Mineralogical analysis, selective extractions, and pore water analysis were a good combination of methods for studying the weathering of tailings and in evaluating metal mobility from the facilities. Selective extractions with visual observations and pH measurements of tailings solids were, nevertheless, adequate in describing the spatial distribution of sulphide oxidation in tailings impoundments. Seepage water chemistry provided additional data on geochemical processes in tailings and was necessary for defining constraints for water treatment.

Determinação de resíduos de cloranfenicol em amostras de leite e mel industrializados utilizando a técnica de espectrometria de massas em "tandem" (CLAE-EM/EM)

The present work shows a method for the determination of chloramphenicol (CAP) antibiotic in milk, powder milk and honey. The solid phase extraction and liquid-liquid extraction were applied as a clean-up and pre-concentration strategies followed by LC-ESI/MS/MS analysis. The recovery was studied for different fortification levels from 0.05 to 1.00 µg L-1 in milk, showing values between 91 101% and RSD bellow 8.0%, while honey was spiked with a concentration of 0.20 µg kg-1 yelding a mean recovery of 83% and RSD of 6.5%. The quantification transition 321>152 showed a LOD of 0.52 ng kg-1 and LOQ of 1.85 ng kg-1.

Novos sorventes baseados em poli (metiloctilsiloxano) sobre sílica para uso em extração em fase sólida

This paper presents an easy and practical procedure to obtain silica-based C-8 type sorbents for use in solid-phase extraction. The materials are prepared by depositing poly(methyloctylsiloxane), PMOS, on the silica support. Two different treatments for immobilization were used: thermal treatment or gamma irradiation. Suitable recoveries were obtained after pre-concentration of dilute solutions, at the ng/L level, of a mixture of pesticides, indicating the good performance of the materials.

Counter-current Washing of Filter Cakes

The main objective of this thesis was to compare the efficiency of counter-current and co-current filter cake washing techniques. Filter cake washing is a common unit operation which is used in the chemical process industry for improving the recovery of the liquid phase or for purifying the solid phase of the filter cake. Counter-current displacement washing is more difficult to arrange and it requires additional process equipment but the advantage of counter-current method is that the consumption of wash water that is required for achieving certain filter cake purity may be considerably decreased when compared to the co-current washing method. This is true especially for materials that are difficult to wash. The literature part of this thesis consists of a review of filter cake washing in general, including the basic principles of co-current and counter-current techniques, and a description of the structure and operation of a horizontal vacuum belt filter, which is the equipment considered in the experimental part of this thesis. Also the most common cake washing models are introduced. The experiments were performed by washing wheat apatite filter cakes in a laboratory scale vacuum filter by using both co-current and counter-current washing methods. The main results of these tests were the washing curves that relate the purity of the filter cake to the amount of wash liquid used. Comparison between the obtained washing curves showed that both washing methods could be efficiently applied for achieving good washing results. The differences between the wash liquid consumptions in the co-current and counter-current washing methods were found to be surprisingly small but this is most probably explained by the relatively good washing characteristics of the apatite cakes. The washing models introduced in the literature part were compared with the results obtained from the experiments and it was found out that the studied cake washing processes could be described

Quantificação de sulfadimetoxina em leite por cromatografia líquida de alta eficiência

A method for HPLC determination of sulfadimethoxyne in milk is presented. The analyte isolation and concentration were performed by solid-phase extraction through a C-8 cartridge, pre-conditioned with hexane, methanol and water and eluted with MeOH. The recovery determination was done with a spiked solution of 20, 50 or 100 µg L-1. In this concentration range, the recovery was 83.2% with a RDS of 15.4%. For quantification, a Zorbax Eclipse XDB-C8 (4.6 mm x 150 mm, 5 µm), a mobile phase of MeCN: 0.01 mol L-1 KH2PO4 aq. (1:4), and a variable wavelength detector (275 nm) were used.

Pré-concentração de cádmio com Saccharomyces cerevisiae e determinação em águas fluviais usando espectrometria de emissão óptica com plasma indutivamente acoplado

A preconcentration method based on the use of Saccharomyces cerevisiae as sorbent material is proposed for the determination of Cd(II) in river water. The solid phase extraction was performed in batch mode and the determination of the analyte in the solid phase was easily carried out by introducing a slurry of the yeast (0.0625 g / 2.5 mL) directly into the ICP OES. A limit of detection of 0.11 µg L-1 and a sample throughput in the range of 4 - 54 sample h-1 were obtained. Determinations of cadmium in a certified sample and in real river water samples were in excellent agreement with the expected values.

Obtenção de titânio metálico com porosidade controlada por metalurgia do pó

Titanium is an attractive material for structural and biomedical applications because of its excellent corrosion resistance, biocompatibility and high strength-to-weight ratio. The high reactivity of titanium in the liquid phase makes it difficult to produce it by fusion. Powder metallurgy has been shown to be an adequate technique to obtain titanium samples at low temperatures and solid-phase consolidation. The production of compacts with different porosities obtained by uniaxial pressing and vacuum sintering is briefly reviewed. Powder particle size control has been shown to be very important for porosity control. Sample characterization was made using scanning electron microscopy (SEM) images.

Utilização da extração em fase sólida (SPE) na determinação de hidrocarbonetos policíclicos aromáticos em matrizes aquosas ambientais

Polycyclic aromatic hydrocarbons (PAHs) are a great environmental concern mainly because of their toxic, mutagenic and carcinogenic potential. This paper reports utilization of the solid-phase extraction (SPE) technique to determine PAHs in environmental aqueous matrices. The recovery from environmental aqueous matrices fortified with PAHs varied from 63.7 to 93.1% for atmospheric liquid precipitation, from 38.3 to 95.1% for superficial river water, and from 71.0 to 95.5% for marine water. No negative matrix effect was observed for the recovery of PAHs from atmospheric liquid precipitation and marine water, but was observed for superficial river water, particularly for PAHs possessing 5 and 6 aromatic rings.

Desenvolvimento de um método empregando quitosana para remoção de íons metálicos de águas residuárias

In this work a method was developed for removing metallic ions from wastewaters by co-precipitation of Cu2+, Pb2+, Cd2+, Cr3+ and Hg2+ with chitosan and sodium hydroxide solution. Solutions of these metallic ions in the range from 0.55 to 2160 mg L-1 were added to chitosan dissolved in 0.05 mol L-1 HCl. For the co-precipitation of metal-chitosan-hydroxide a 0.17 mol L-1 NaOH solution was added until pH 8.5-9.5. A parallel study was carried out applying a 0.17 mol L-1 NaOH solution to precipitate those metallic ions. Also, a chitosan solid phase column was used for removing those metallic ions from wastewaters.

Efecto de la naturaleza del precursor sobre las caracteristicas de las nanoparticulas de SnO2 sintetizadas

Tin oxide (SnO2) is widely used in industry as raw material for electronic devices, plating of different types of materials, for dyes and pigments, for electroplating, heterogeneous catalysis, etc. In this work SnO2 was obtained by a controlled precipitation method with special attention to the effects the tin precursor has on the microstructure of the final product. The most appropriate pH for obtaining SnO2 with the rutile structure as the main phase is 6.25 for SnCl2 and 6.40 for SnSO4. After heat treatment at 600 °C, particles of nanometric order (~10 - 30 nm approx) were obtained. The characterization of the solid phase was made by X-ray diffraction (XRD), thermal analysis (DTA/TG), transmission electron microscopy (TEM) and Fourier transformed infrared spectroscopy (FTIR).

Determinação do coeficiente de atividade na diluição infinita (g¥) através da micro-extração em fase sólida (SPME)

In this study a new approach, solid phase micro extraction (SPME), is used in the evaluation of the infinite dilution activity coefficient of the solute in a given solvent. It is the purpose of the current work to demonstrate a different approach to obtain the data needed for studying the solution thermodynamics of binary liquid mixtures as well as for designing multi-component separations. The solutes investigated at the temperature 298.15 K were toluene, ethyl benzene and xylene in the solvent methanol.

Investigation of the occurrence of pesticide residues in rural wells and surface water following application to tobacco

In this work the exposure of wells and surface water to pesticides, commonly used for tobacco cropping, was assessed. Water consumption wells and surface water flows were sampled at different times. After a preconcentration step with solid phase extraction (SPE), the selected pesticides were determined by gas chromatography with electron capture detection (GC-ECD) or high performance liquid chromatography with diode array detection (HPLC-DAD). No pesticides were detected in the well water samples and surface water flow in the winter season. However, in the spring and summer higher concentrations of chlorpyrifos and imidacloprid were found in the water source samples. Atrazine, simazine and clomazone were also found. The occurrence of pesticides in collected water samples was related with the application to tobacco.

Un método de bajo costo para la determinación de cobre a nivel de vestigios en matrices de interés ambiental por espectrofotometría en fase sólida (EFS)

A method for determining copper by solid phase spectrophotometry (SPS) was optimized using the Doehlert design. Copper(II) was sorbed on a styrene-divinylbenzene anion-exchange resin as a Cu(II)-1-(2-pyridylazo)-2-naphthol (PAN) complex, at pH 7.0. Resin phase absorbances at 560 and 800 nm were measured directly. The detection limit was found to be 2.5 µg L-1. The relative standard deviation on ten replicate determinations of 10 µg Cu(II) in 1000 mL samples was 1.1%. The linear range of the determination was 5.0-100 µg L-1. The method was applied successfully to the determination of Cu(II) in natural water and vegetable samples.