Oxidative Leaching of metals from electronic waste with solutions based on quaternary ammonium salts

The treatment of electric and electronic waste (WEEE) is a problem which receives ever more attention. An inadequate treatment results in harmful products ending up in the environment. This project intends to investigate the possibilities of an alternative route for recycling of metals from printed circuit boards (PCBs) obtained from rejected computers. The process is based on aqueous solutions composed of an etchant, either 0.2 M CuCl2.2H2O or 0.2 M FeCl3.6H2O, and a quaternary ammonium salt (quat) such as choline chloride or chlormequat. These solutions are reminiscent of deep eutectic solvents (DES) based on quats. DES are quite similar to ionic liquids (ILs) and are used as well as alternative solvents with a great diversity of physical properties, making them attractive for replacement of hazardous, volatile solvents (e.g. VOCs). A remarkable difference between genuine DES and ILs with the solutions used in this project is the addition of rather large quantities of water. It is shown the presence of water has a lot of advantages on the leaching of metals, while the properties typical for DES still remain. The oxidizing capacities of Cu(II) stem from the existence of a stable Cu(I) component in quat based DES and thus the leaching stems from the activity of the Cu(II)/Cu(I) redox couple. The advantage of Fe(III) in combination with DES is the fact that the Fe(III)/Fe(II) redox couple becomes reversible, which is not true in pure water. This opens perspectives for regeneration of the etching solution. In this project the leaching of copper was studied as a function of gradual increasing water content from 0 - 100w% with the same concentration of copper chloride or iron(III) chloride at room temperature and 80ºC. The solutions were also tested on real PCBs. At room temperature a maximum leaching effect for copper was obtained with 30w% choline chloride with 0.2 M CuCl2.2H2O. The leaching effect is still stronger at 80°C, b ut of course these solutions are more energy consuming. For aluminium, tin, zinc and lead, the leaching was faster at 80ºC. Iron and nickel dissolved easily at room temperature. The solutions were not able to dissolve gold, silver, rhodium and platinum.

Desenvolvimento de um sensor óptico para determinação de Norfloxacina

A presente dissertação descreve o desenvolvimento e a caracterização de sensores ópticos com base em membranas de poli(cloreto de vinilo), PVC, para determinação de Norfloxacina em amostras do sector da aquacultura. Estes sensores basearam-se na reacção colorimétrica entre um metal imobilizado em PVC e a Norfloxacina. O metal foi escolhido com base em ensaios prévios de reacção colorimétrica entre a Norfloxacina e várias espécies metálicas, nomeadamente, Fe(III), Al(III), Pb(II), Aluminon, Mo(II), Mn(II), Ni(II), Cu(II), Co(II), Sn(II) e V(V). A reacção mais intensa foi obtida com o Fe(III). Neste sentido, numa primeira fase foram desenvolvidos sensores baseados em Fe(III). O efeito de alguns parâmetros experimentais na resposta desses sensores foi avaliado de modo univariado. Incluem-se aqui o efeito do pH, avaliado entre 2,00 e 6,00, e o da concentração de Fe(III), variada entre cerca de 1,00x10-5 M e 2,00x10-4 M. Os melhores valores foram obtidos a pH 3, para o qual se verificou um comportamento linear entre cerca de 1,00x10-5 M e 1,70x10-4 M de Fe(III). Utilizando as condições seleccionadas anteriormente, procedeu-se à caracterização do complexo sob ponto de vista químico. Os valores obtidos apontaram para a necessidade de um excesso de Fe(III) de, pelo menos, 10 vezes, no sentido de garantir a máxima extensão de complexação. O complexo referido apresentou, nestas condições, um comportamento linear ao longo do intervalo de concentrações de cerca de 7,00x10-5 M a 7,00x10-4 M em NOR. O complexo formado foi estável ao longo de 90 minutos. As condições óptimas para análise desse complexo numa superfície sólida foram obtidas após avaliação do efeito da quantidade de Fe(III) e do tipo e quantidade de solvente mediador (o-nitrofenil octil éter, di-n-octilftalato, dibutilftalato, bis(etilhexil)sebacato, bis(etilhexil)ftalato). O bis(etilhexil)sebacato foi o solvente mediador escolhido e a relação de quantidade entre o PVC e o solvente mediador foi igual a 1:2. O procedimento de preparação do sensor sólido e subsequente optimização foi aplicado a outras espécies metálicas, para além do Fe(III), tais como, Cu(II), Mn(II) e aluminon. A conjugação de todos estes metais permitiu desenvolver um array de sensores para despistagem de Norfloxacina em águas de aquacultura. Algumas membranas sensoras foram aplicadas com sucesso no controlo de Norfloxacina em amostras de águas ambientais dopadas. Os resultados obtidos com membranas de Fe(III) e Cu(II) foram exactos, tendo-se registado valores de concentração próximos dos reais. O método proposto permitiu, por isso, a despistagem rápida e eficaz da presença de um antibiótico em águas ambientais, permitindo ainda o seu doseamento a um baixo custo. Numa perspectiva de rotina, e tendo em vista a despistagem deste antibiótico, este método revelou-se mais rápido e mais barato do que os demais métodos descritos na literatura para este efeito.

Voltammetric oxidation of drugs of abuse II. Codeine and metabolites

The oxidation of codeine on glassy carbon electrodes has been studied in detail using differential pulse voltammetry. The results obtained using a glassy carbon electrode clearly show a much more complex oxidation mechanism than that previously reported when platinum and gold electrodes were used. To clarify the codeine oxidative profile, several metabolites and analogues of this alkaloid, codeine N-oxide, norcodeine, dihydrocodeine, acetylcodeine and 6- chlorodesoxycodeine, were synthesized and studied. It was deduced that the anodic waves observed in codeine oxidation are related to the presence of methoxy, hydroxy and tertiary amine groups. Due to the similarity of potentials at which these oxidative processes take place, at some pHs an overlap of peaks occurs and only one anodic wave is observed.

Removal of Cd(II), Zn(II) and Pb(II) from aqueous solutions by brown marine macro algae: kinetic modelling

Specific marine macro algae species abundant at the Portuguese coast (Laminaria hyperborea, Bifurcaria bifurcata, Sargassum muticum and Fucus spiralis) were shown to be effective for removing toxic metals (Cd(II), Zn(II) and Pb(II)) from aqueous solutions. The initial metal concentrations in solution were about 75–100 mg L−1. The observed biosorption capacities for cadmium, zinc and lead ions were in the ranges of 23.9–39.5, 18.6–32.0 and 32.3–50.4 mg g−1, respectively. Kinetic studies revealed that the metal uptake rate was rather fast, with 75% of the total amount occurring in the first 10 min for all algal species. Experimental data were well fitted by a pseudo-second order rate equation. The contribution of internal diffusion mechanism was significant only to the initial biosorption stage. Results indicate that all the studied macro algae species can provide an efficient and cost-effective technology for eliminating heavy metals from industrial effluents.

Ecotoxicity tests using the green algae chlorella vulgaris — a useful tool in hazardous effluents management

The treatment efficiency of laboratory wastewaters was evaluated and ecotoxicity tests with Chlorella vulgaris were performed on them to assess the safety of their environmental discharge. For chemical oxygen demand wastewaters, chromium (VI), mercury (II) and silver were efficiently removedby chemical treatments.Areduction of ecotoxicitywas achieved; nevertheless, an EC50 (effective concentration that causes a 50% inhibition in the algae growth) of 1.5% (v/v) indicated still high level of ecotoxicity. For chloride determination wastewaters, an efficient reduction of chromium and silver was achieved after treatment. Regarding the reduction of ecotoxicity observed, EC50 increased from 0.059% to 0.5%, only a 0.02% concentration in the aquatic environment would guarantee no effects. Wastewaters containing phenanthroline/iron (II) complex were treated by chemical oxidation. Treatmentwas satisfactory concerning chemical parameters, although an increase in ecotoxicitywas observed (EC50 reduced from 0.31% to 0.21%). The wastes from the kinetic study of persulphate and iodide reaction were treated with sodium bisulphite until colour was removed. Although they did not reveal significant ecotoxicity, only over 1% of the untreated waste produced observable effects over algae. Therefore, ecotoxicity tests could be considered a useful tool not only in laboratory effluents treatment, as shown, but also in hazardous wastewaters management.

Optimization of Cu(II) biosorption onto ascophyllum nodosum by factorial design methodology

A Box–Behnken factorial design coupled with surface response methodology was used to evaluate the effects of temperature, pH and initial concentration in the Cu(II) sorption process onto the marine macroalgae Ascophyllum nodosum. The effect of the operating variables on metal uptake capacitywas studied in a batch system and a mathematical model showing the influence of each variable and their interactions was obtained. Study ranges were 10–40ºC for temperature, 3.0–5.0 for pH and 50–150mgL−1 for initial Cu(II) concentration. Within these ranges, the biosorption capacity is slightly dependent on temperature but markedly increases with pH and initial concentration of Cu(II). The uptake capacities predicted by the model are in good agreement with the experimental values. Maximum biosorption capacity of Cu(II) by A. nodosum is 70mgg−1 and corresponds to the following values of those variables: temperature = 40ºC, pH= 5.0 and initial Cu(II) concentration = 150mgL−1.

Soil remediation time to achieve clean-up goals II: influence of natural organic matter and water contents

This work reports a relatively rapid procedure for the forecasting of the remediation time (RT) of sandy soils contaminated with cyclohexane using vapour extraction. The RT estimated through the mathematical fitting of experimental results was compared with that of real soils. The main objectives were: (i) to predict the RT of soils with natural organic matter (NOM) and water contents different from those used in experiments; and (ii) to analyse the time and efficiency of remediation, and the distribution of contaminants into the soil matrix after the remediation process, according to the soil contents of: (ii1) NOM; and (ii2) water. For sandy soils with negligible clay contents, artificially contaminated with cyclohexane before vapour extraction, it was concluded that: (i) if the NOM and water contents belonged to the range of the prepared soils, the RT of real soils could be predicted with relative differences not higher than 12%; (ii1) the increase of NOM content from 0% to 7.5% increased the RT (1.8–13 h) and decreased the remediation efficiency (RE) (99–90%) and (ii2) the increase of soil water content from 0% to 6% increased the RT (1.8–4.9 h) and decreased the RE (99–97%). NOM increases the monolayer capacity leading to a higher sorption into the solid phase. Increasing of soil water content reduces the mass transfer coefficient between phases. Concluding, NOM and water contents influence negatively the remediation process, turning it less efficient and more time consuming, and consequently more expensive.

Optical fiber sensor for Hg(II) based on carbon dots

An optical fiber sensor for Hg(II) in aqueous solution based on sol–gel immobilized carbon dots nanoparticles functionalized with PEG200 and N-acetyl-l-cysteine is described. This sol–gel method generated a thin (about 750 nm), homogenous and smooth (roughness of 2.7±0.7 a˚ ) filmthat immobilizes the carbon dots and allows reversible sensing of Hg(II) in aqueous solution. A fast (less than 10 s), reversible and stable (the fluorescence intensity measurements oscillate less than 1% after several calibration cycles) sensor system was obtained. The sensor allow the detection of submicron molar concentrations of Hg(II) in aqueous solution. The fluorescence intensity of the immobilized carbon dots is quenched by the presence of Hg(II) with a Stern-Volmer constant (pH = 6.8) of 5.3×105M−1.

Flow-injection potentiometric method for the routine determination of chloride: application to bread analysis

Bread is consumed worldwide by man, thus contributing to the regular ingestion of certain inorganic species such as chloride. It controls the blood pressure if associated to a sodium intake and may increase the incidence of stomach ulcer. Its routine control should thus be established by means of quick and low cost procedures. This work reports a double- channel flow injection analysis (FIA) system with a new chloride sensor for the analysis of bread. All solutions are prepared in water and necessary ionic strength adjustments are made on-line. The body of the indicating electrode is made from a silver needle of 0.8 mm i.d. with an external layer of silver chloride. These devices were constructed with different lengths. Electrodes of 1.0 to 3.0 cm presented better analytical performance. The calibration curves under optimum conditions displayed Nernstian behaviour, with average slopes of 56 mV decade-1, with sampling rates of 60 samples h-1. The method was applied to analyze several kinds of bread, namely pão de trigo, pão integral, pão de centeio, pão de mistura, broa de milho, pão sem sal, pão meio sal, pão-de-leite, and pão de água. The accuracy and precision of the potentiometric method were ascertained by comparison to a spectrophotometric method of continuous segmented flow. These methods were validated against ion-chromatography procedures.

Adding value [valorization] to tannery fleshings: part II – effect of protein hydrolysates on leather dyeing

The tanning industry generates a high quantity of solid wastes. Therefore, there is a need to create valorization [added value] options for these wastes. The main objective of the present work was to study the effect of protein hydrolysates (HP) prepared from fleshings on leather dyeing. During previous studies it was found that the application of HP products, obtained from fleshings, in leather retannage intensified the colour of crust leather. In this work the CIELAB colour system was used to evaluate the effect of HP on retannage processes. The main conclusions of this study were: (i) HP can be used instead of a dicyanodiamide resin (Fortan DC) if the colour parameters of the standard procedure are to be maintained, and (ii) the replacement of an acrylic resin (Fortan A40) by glutaraldehyde-modified HP (GHP) results in a darker skin, and can therefore be interesting for the reduction of the quantity of dye used.

Assessment of the potential of tin sulphide thin films prepared by sulphurization of metallic precursors as cell absorbers

In this work, SnxSy thin films have been grown on soda-lime glass substrates by sulphurization of metallic precursors in a nitrogen plus sulphur vapour atmosphere. Different sulphurization temperatures were tested, ranging from 300 °C to 520 °C. The resulting phases were structurally investigated by X-Ray Diffraction and Raman spectroscopy. Composition was studied using Energy Dispersive Spectroscopy being then correlated with the sulphurization temperature. Optical measurements were performed to obtain transmittance and reflectance spectra, from which the energy band gaps, were estimated. The values obtained were 1.17 eV for the indirect transition and for the direct transition the values varied from 1.26 eV to 1.57 eV. Electrical characterization using Hot Point Probe showed that all samples were p-type semiconductors. Solar cells were built using the structure: SLG/Mo/SnxSy/CdS/ZnO:Ga and the best result for solar cell efficiency was 0.17%.

Interlaminar fracture characterization of a carbon-epoxy composite in pure mode II

The interlaminar fracture toughness in pure mode II (GIIc) of a Carbon-Fibre Reinforced Plastic (CFRP) composite is characterized experimentally and numerically in this work, using the End-Notched Flexure (ENF) fracture characterization test. The value of GIIc was extracted by a new data reduction scheme avoiding the crack length measurement, named Compliance-Based Beam Method (CBBM). This method eliminates the crack measurement errors, which can be non-negligible, and reflect on the accuracy of the fracture energy calculations. Moreover, it accounts for the Fracture Process Zone (FPZ) effects. A numerical study using the Finite Element Method (FEM) and a triangular cohesive damage model, implemented within interface finite elements and based on the indirect use of Fracture Mechanics, was performed to evaluate the suitability of the CBBM to obtain GIIc. This was performed comparing the input values of GIIc in the numerical models with the ones resulting from the application of the CBBM to the numerical load-displacement (P-) curve. In this numerical study, the Compliance Calibration Method (CCM) was also used to extract GIIc, for comparison purposes.

Recovery of acid and base from brackish water by bipolar membrane electrodialysis

Nesta dissertação pretendeu-se estudar a viabilidade do uso de eletrodiálise com membranas bipolares (BM) na recuperação de ácido clorídrico e de hidróxido de sódio a partir de um efluente industrial que contém 1.4 mol/L de cloreto de sódio. Estas membranas mostraram ser uma ferramenta eficiente para a produção de ácidos e bases a partir do respetivo sal. Foi feita uma seleção de diferentes membranas bipolares (Neosepta, Fumatech e PCA) e aniónicas (PC-SA e PC-ACID 60) na tentativa de encontrar a combinação mais adequada para o tratamento do efluente. Dependendo do critério, o melhor arranjo de membranas é o uso de PC-ACID 60 (membrana aniónica), PC-SK (membrana catiónica) e membranas bipolares do tipo Neosepta para maior pureza dos produtos; membranas bipolares Fumatech para maior eficiência de dessalinização e membranas bipolares PCA para um maior grau de dessalinização. Tecnologicamente foi possível obter uma dessalinização de 99.8% em quatro horas de funcionamento em modo batch com recirculação de todas as correntes. Independentemente da combinação usada é recomendável que o processo seja parado quando a densidade de corrente deixa de ser máxima, 781 A/m2. Assim é possível evitar o aumento de impurezas nos produtos, contra difusão, descida instantânea do pH e uma dessalinização pouco eficiente. A nível piloto o principal fornecedor de membranas e unidade de tratamento “stack” é a marca alemã PCA. Sendo assim realizaram-se ensaios de repetibilidade, contra difusão, avaliação económica e upscaling utilizando as membranas bipolares PCA. A nível económico estudou-se o uso de dois tipos de unidades de tratamento; EDQ 380 e EDQ 1600, para diferentes níveis de dessalinização (50, 75 e 80%). Tendo em conta a otimização económica, é recomendável uma dessalinização máxima de 80%, uma vez que a eficiência de processo a este ponto é de 40%. A aplicação do método com a unidade EDQ 1600 para uma dessalinização de 50% é a mais vantajosa economicamente, com custos de 16 €/m3 de efluente tratado ou 0,78 €/kg Cl- removido. O número de unidades necessárias é 4 posicionados em série.

European Union emissions trading scheme impact on the Spanish electricity price during phase II and phase III implementation

The European Union Emissions Trading Scheme (EU ETS) is a cornerstone of the European Union's policy to combat climate change and its key tool for reducing industrial greenhouse gas emissions cost-effectively. The purpose of the present work is to evaluate the influence of CO2 opportunity cost on the Spanish wholesale electricity price. Our sample includes all Phase II of the EU ETS and the first year of Phase III implementation, from January 2008 to December 2013. A vector error correction model (VECM) is applied to estimate not only long-run equilibrium relations, but also short-run interactions between the electricity price and the fuel (natural gas and coal) and carbon prices. The four commodities prices are modeled as joint endogenous variables with air temperature and renewable energy as exogenous variables. We found a long-run relationship (cointegration) between electricity price, carbon price, and fuel prices. By estimating the dynamic pass-through of carbon price into electricity price for different periods of our sample, it is possible to observe the weakening of the link between carbon and electricity prices as a result from the collapse on CO2 prices, therefore compromising the efficacy of the system to reach proposed environmental goals. This conclusion is in line with the need to shape new policies within the framework of the EU ETS that prevent excessive low prices for carbon over extended periods of time.