Genotoxicity in humans and indicator species exposed to uranium wastes

Os riscos dos resíduos provenientes da extração do urânio estão associados ao seu conteúdo em metais e radionuclídeos, o que levanta preocupações às autoridades governamentais e à população em geral. As populações humanas e outras espécies animais que vivem em zonas de exploração de urânio poderão estar expostas à radiação através de resíduos e poeiras radioactivase também através de água e alimentos contaminados. A determinação dos riscos deste tipo de contaminantes é feita, principalmente, através da análise química de amostras ambientais, dando-se menos importância à determinação de efeitos biológicos. A determinação de efeitos biológicos causados pela exposição a poluentes, tem-se revelado muito importante para uma avaliação da qualidade ambiental, de modo a providenciar indicações acerca dos efeitos negativos nos seres vivos e também para complementar a informação dada pelas análises químicas de amostras ambientais. Este facto levou ao estabelecimento de biomarcadores, que consistem em respostas biológicas adversas que são específicas de uma exposição a toxinas ambientais, para serem usadas como ferramentas de avaliação da qualidade ambiental. Neste trabalho foram analisadas respostas a nível molecular e celular, em minhocas, ratinhos do campo e humanos, a fim de determinar o risco químico e radiológico dos resíduos provenientes da mina de urânio da Cunha Baixa. Este trabalho teve também como objectivo a clarificação das respostas subjacentes à exposição a metais e radionuclídeos, a fim de permitir o desenvolvimento de potenciais novos biomarcadores moleculares. Durante este trabalho foram efectuados ensaios com minhocas, em que estas foram expostas durante 56 dias a solo contaminado proveniente da mina de urânio da Cunha Baixa, em laboratório e in situ. Durante a exposição foram analisados vários parâmetros, como o crescimento, reprodução, bioacumulação de metais e radionuclídeos, histopatologia, danos no DNA, citotoxicidade e perfil de expressão genética. Para além disso, foram amostrados ratinhos do campo na mina de urânio da Cunha Baixa e numa área de referência para determinação de danos no DNA, níveis de expressão e mutações em genes supressores de tumores e também bioacumulação de metais. Por fim, foram recolhidas amostras de sangue em voluntários saudáveis pertencentes à população da aldeia da Cunha Baixa, para determinação de danos no DNA, imunofenotipagem e quantificação de metais no sangue. Os resultados revelaram que as minhocas assim como os ratinhos do campo foram negativamente afetados pela exposição aos resíduos mineiros em todos os níveis de organização biológica aqui analisados, o que faz destes organismos bons indicadores para a determinação do risco destas áreas contaminadas, evidenciando o potencial risco da exposição a estes contaminantes. Para além disso, o estudo feito à população da Cunha Baixa revelou danos no ADN e diminuição de populações importantes de células imunitárias (nomeadamente linfócitos T e NK), o que poderá resultar da exposição aos resíduos da mina, tornando as pessoas mais susceptíveis ao desenvolvimento de processos de carcinogénese. O presente estudo contribuiu significativamente para a caracterização dos riscos da exposição a resíduos provenientes de minas de urânio abandonadas, evidenciando os seus efeitos negativos a nível molecular e celular, que potencialmente poderão causar instabilidade genómica e aumentar o risco de desenvolvimento de doenças genéticas.

Valorization of solid wastes from cellulose and paper industry

This thesis reports in detail studies of industrial solid wastes valorization as alternative raw materials. All tested wastes are classified as non-hazardous and are generated in the pulp and paper process, including primary sludge, dregs, grits, lime mud and bottom ash (this generated in a process that occurs in parallel to the production of cellulose, whose aim is the production of energy to supply the plant through the combustion of forest biomass in fluidized bed). A detailed general characterization was performed at each waste and according to their characteristics, they were selected some applications in materials with potential use, specifically in Fibercement, Bituminous Mixture for regularization layer and industrial mortars (rendering mortars and cementitious-adhesive). After decided to application each waste was specifically tested to proceed the setting up of formulations containing different content of waste in replacement of the raw conventional material. As an isolated case, the bottom ash was tested not only as an alternative raw material for construction materials, but also it was tested for its use in fluidized bed in which the waste is generated as raw material. Both dregs and bottom ash had undergone special treatment to make possible to obtain a better quality of waste in order do not compromise the final product characteristics and process. The dregs were tested in bituminous mixtures as received and also washed (on the laboratory scale to remove soluble salts) and bottom ash were washed and screened in industrial scale (for removal of soluble salts, especially chlorides and coarse fraction particles elimination - particles larger than 1 mm size). The remaining residues form used in such as received avoiding additional costs. The results indicated potential and some limitations for each application to the use of these wastes as alternative raw material, but in some cases, the benefits in relation to valorization overlap with its limitations in both aspects, environmental and economic.

Development of a sustainable method for the extraction of lycopene and β-carotene from food wastes

The main objective of the present work is the study of a profitable process not only in the extraction and selective separation of lycopene and β-carotene, two compounds present in tomato, but also in its potential application to food industry wastes. This is one of the industries that produce larger amounts of wastes, which are rich in high value biomolecules with great economic interest. However, the conventional methods used to extract this kind of compounds are expensive which limits their application at large scale. Lycopene and βcarotene are carotenoids with high commercial value, known for their antioxidant activity and benefits to human health. Their biggest source is tomato, one of the world’s most consumed fruits, reason for which large quantities of waste is produced. This work focuses on the study of diverse solvents with a high potential to extract carotenoids from tomato, as well as the search for more environmentally benign solvents than those currently used to extract lycopene and β-carotene from biomass. Additionally, special attention was paid to the creation of a continuous process that would allow the fractionation of the compounds for further purification. Thus, the present work started with the extraction of both carotenoids using a wide range of solvents, namely, organic solvents, conventional salts, ionic liquids, polymers and surfactants. In this stage, each solvent was evaluated in what regards their capacity of extraction as well as their penetration ability in biomass. The results collected showed that an adequate selection of the solvents may lead to the complete extraction of both carotenoids in one single step, particularly acetone and tetrahydrofuran were the most effective ones. However, the general low penetration capacity of salts, ionic liquids, polymers and surfactants makes these solvents ineffective in the solid-liquid extraction process. As the organic solvents showed the highest capacity to extract lycopene and βcarotene, in particular tetrahydrofuran and acetone, the latter solvent used in the development process of fractionation, using to this by strategic use of solvents. This step was only successfully developed through the manipulation of the solubility of each compound in ethanol and n-hexane. The results confirmed the possibility of fractionating the target compounds using the correct addition order of the solvents. Approximately, 39 % of the β-carotene was dissolved in ethanol and about 64 % of lycopene was dissolved in n-hexane, thus indicating their separation for two different solvents which shows the selective character of the developed process without any prior stage optimization. This study revealed that the use of organic solvents leads to selective extraction of lycopene and β-carotene, allowing diminishing the numerous stages involved in conventional methods. At the end, it was possible to idealize a sustainable and of high industrial relevance integrated process, nevertheless existing the need for additional optimization studies in the future.

Galvanic Vestibular Stimulation Induces a Spatial Bias in Whole-body Position Estimates

Letter to the Editor

Bio-synthesis of nanosized semiconductors using mine wastes as material sources

This work describes the synthesis of nanosized metal sulfides and respective SiO2 and/or TiO2 composites in high yield via a straightforward process, under ambient conditions (temperature and pressure), by adding to aqueous metals a nutrient solution containing biologically generated sulfide from sulfate-reducing bacteria (SRB). The nanoparticles‘ (NPs) morphological properties were shown not to be markedly altered by the SRB growth media composition neither by the presence of bacterial cells. We further extended the work carried out, using the effluent of a bioremediation system previously established. The process results in the synthesis of added value products obtained from metal rich effluents, such as Acid Mine Drainage (AMD), when associated with the bioremediation process. Precipitation of metals using sulfide allows for the possibility of selective recovery, as different metal sulfides possess different solubilities. We have evaluated the selective precipitation of CuS, ZnS and FeS as nanosized metal sulfides. Again, we have also tested the precipitation of these metal sulfides in the presence of support structures, such as SiO2. Studies were carried out using both artificial and real solutions in a continuous bioremediation system. We found that this method allowed for a highly selective precipitation of copper and a lower selectivity in the precipitation of zinc and iron, though all metals were efficiently removed (>93% removal). This research has also demonstrated the potential of ZnS-TiO2 nanocomposites as catalysts in the photodegradation of organic pollutants using the cationic dye, Safranin-T, as a model contaminant. The influence of the catalyst amount, initial pH and dye concentration were also evaluated. Finally, the efficiency of the precipitates as catalysts in sunlight mediated photodegradation was investigated, using different volumes of dye-contaminated water (150 mL and 10 L). This work demonstrates that all tested composites have the potential to be used as photocatalysts for the degradation of Safranin-T.

Determination of the Maximum Rate of Eccrine Sweat Glands’ Ion Reabsorption Using the Galvanic Skin Conductance to Local Sweat Rate Relationship

Purpose The purpose of the present study was to develop and describe a simple method to evaluate the rate of ion reabsorption of eccrine sweat glands in human using the measurement of galvanic skin conductance (GSC) and local sweating rate (SR). This purpose was investigated by comparing the SR threshold for increasing GSC with following two criteria of sweat ion reabsorption in earlier studies such as 1) the SR threshold for increasing sweat ion was at approximately 0.2 to 0.5 mg/cm2/min and 2) exercise-heat acclimation improved the sweat ion reabsorption ability and would increase the criteria 1. Methods Seven healthy non-heat-acclimated male subjects received passive heat treatment both before and after 7 days of cycling in hot conditions (50% maximum oxygen uptake, 60 min/day, ambient temperature 32°C, and 50% relative humidity). Results Subjects became partially heat-acclimated, as evidenced by the decreased end-exercise heart rate (p<0.01), rate of perceived exhaustion (p<0.01), and oesophageal temperature (p=0.07), without alterations in whole-body sweat loss, from the first to the last day of training. As hypothesised, we confirmed that the SR threshold for increasing GSC was near the predicted SR during passive heating before exercise heat acclimation, and increased significantly after training (0.19 ± 0.09 to 0.32 ± 0.10 mg/cm2/min, p<0.05). Conclusions The reproducibility of sweat ion reabsorption by the eccrine glands in the present study suggests that the relationship between GSC and SR can serve as a new index for assessing the maximum rate of sweat ion reabsorption of eccrine sweat glands in humans.

An integrated recycling approach for GFRP pultrusion wastes: recycling and reuse assessment into new composite materials using Fuzzy Boolean Nets

In this study, efforts were made in order to put forward an integrated recycling approach for the thermoset based glass fibre reinforced polymer (GPRP) rejects derived from the pultrusion manufacturing industry. Both the recycling process and the development of a new cost-effective end-use application for the recyclates were considered. For this purpose, i) among the several available recycling techniques for thermoset based composite materials, the most suitable one for the envisaged application was selected (mechanical recycling); and ii) an experimental work was carried out in order to assess the added-value of the obtained recyclates as aggregates and reinforcement replacements into concrete-polymer composite materials. Potential recycling solution was assessed by mechanical behaviour of resultant GFRP waste modified concrete-polymer composites with regard to unmodified materials. In the mix design process of the new GFRP waste based composite material, the recyclate content and size grade, and the effect of the incorporation of an adhesion promoter were considered as material factors and systematically tested between reasonable ranges. The optimization process of the modified formulations was supported by the Fuzzy Boolean Nets methodology, which allowed finding the best balance between material parameters that maximizes both flexural and compressive strengths of final composite. Comparing to related end-use applications of GFRP wastes in cementitious based concrete materials, the proposed solution overcome some of the problems found, namely the possible incompatibilities arisen from alkalis-silica reaction and the decrease in the mechanical properties due to high water-cement ratio required to achieve the desirable workability. Obtained results were very promising towards a global cost-effective waste management solution for GFRP industrial wastes and end-of-life products that will lead to a more sustainable composite materials industry.

Re-use assessment of thermoset composite wastes as aggregate and filler replacement for concrete-polymer composite materials: a case study regarding GFRP pultrusion wastes

Glass fibre-reinforced plastics (GFRP), nowadays commonly used in the construction, transportation and automobile sectors, have been considered inherently difficult to recycle due to both the cross-linked nature of thermoset resins, which cannot be remoulded, and the complex composition of the composite itself, which includes glass fibres, polymer matrix and different types of inorganic fillers. Hence, to date, most of the thermoset based GFRP waste is being incinerated or landfilled leading to negative environmental impacts and additional costs to producers and suppliers. With an increasing awareness of environmental matters and the subsequent desire to save resources, recycling would convert an expensive waste disposal into a profitable reusable material. In this study, the effect of the incorporation of mechanically recycled GFRP pultrusion wastes on flexural and compressive behaviour of polyester polymer mortars (PM) was assessed. For this purpose, different contents of GFRP recyclates (0%, 4%, 8% and 12%, w/w), with distinct size grades (coarse fibrous mixture and fine powdered mixture), were incorporated into polyester PM as sand aggregates and filler replacements. The effect of the incorporation of a silane coupling agent was also assessed. Experimental results revealed that GFRP waste filled polymer mortars show improved mechanical behaviour over unmodified polyester based mortars, thus indicating the feasibility of GFRP waste reuse as raw material in concrete-polymer composites.

Reusability assessment of thermoset polymeric composite wastes as reinforcement and filler replacement for polymer concrete materials

The development and applications of thermoset polymeric composites, namely fiber reinforced polymers (FRP), have shifted in the last decades more and more into the mass market [1]. Production and consume have increased tremendously mainly for the construction, transportation and automobile sectors [2, 3]. Although the many successful uses of thermoset composite materials, recycling process of byproducts and end of lifecycle products constitutes a more difficult issue. The perceived lack of recyclability of composite materials is now increasingly important and seen as a key barrier to the development or even continued used of these materials in some markets.

New recycling approaches for thermoset polymeric composite wastes – an experimental study on polyester based concrete materials filled with fibre reinforced plastic recyclates

In this study, a new waste management solution for thermoset glass fibre reinforced polymer (GFRP) based products was assessed. Mechanical recycling approach, with reduction of GFRP waste to powdered and fibrous materials was applied, and the prospective added-value of obtained recyclates was experimentally investigated as raw material for polyester based mortars. Different GFRP waste admixed mortar formulations were analyzed varying the content, between 4% up to 12% in weight, of GFRP powder and fibre mix waste. The effect of incorporation of a silane coupling agent was also assessed. Design of experiments and data treatment was accomplished through implementation of full factorial design and analysis of variance ANOVA. Added value of potential recycling solution was assessed by means of flexural and compressive loading capacity of GFRP waste admixed mortars with regard to unmodified polymer mortars. The key findings of this study showed a viable technological option for improving the quality of polyester based mortars and highlight a potential cost-effective waste management solution for thermoset composite materials in the production of sustainable concrete-polymer based products.

PLSR Models for Mechanical Strengths of Concrete Composite Materials Reinforced with Pultrusion Wastes

In this paper, we present two Partial Least Squares Regression (PLSR) models for compressive and flexural strength responses of a concrete composite material reinforced with pultrusion wastes. The main objective is to characterize this cost-effective waste management solution for glass fiber reinforced polymer (GFRP) pultrusion wastes and end-of-life products that will lead, thereby, to a more sustainable composite materials industry. The experiments took into account formulations with the incorporation of three different weight contents of GFRP waste materials into polyester based mortars, as sand aggregate and filler replacements, two waste particle size grades and the incorporation of silane adhesion promoter into the polyester resin matrix in order to improve binder aggregates interfaces. The regression models were achieved for these data and two latent variables were identified as suitable, with a 95% confidence level. This technological option, for improving the quality of GFRP filled polymer mortars, is viable thus opening a door to selective recycling of GFRP waste and its use in the production of concrete-polymer based products. However, further and complementary studies will be necessary to confirm the technical and economic viability of the process.

An experimental study on recycling and reuse of pultruded composite material wastes

Glass fibre-reinforced plastics (GFRP) have been considered inherently difficult to recycle due to both: cross-linked nature of thermoset resins, which cannot be remoulded, and complex composition of the composite itself. Presently, most of the GFRP waste is landfilled leading to negative environmental impacts and supplementary added costs. With an increasing awareness of environmental matters and the subsequent desire to save resources, recycling would convert an expensive waste disposal into a profitable reusable material. In this study, efforts were made in order to recycle grinded GFRP waste, proceeding from pultrusion production scrap, into new and sustainable composite materials. For this purpose, GFRP waste recyclates, were incorporated into polyester based mortars as fine aggregate and filler replacements at different load contents and particle size distributions. Potential recycling solution was assessed by mechanical behaviour of resultant GFRP waste modified polymer mortars. Results revealed that GFRP waste filled polymer mortars present improved flexural and compressive behavior over unmodified polyester based mortars, thus indicating the feasibility of the GFRP industrial waste reuse into concrete-polymer composite materials.

A case study undertaken recycling & reuse of glass fiber reinforced thermoset polumer wastes of composite materials industry

Glass fibre-reinforced plastics (GFRP) have been considered inherently difficult to recycle due to both: crosslinked nature of thermoset resins, which cannot be remoulded, and complex composition of the composite itself. Presently, most of the GFRP waste is landfilled leading to negative environmental impacts and supplementary added costs. With an increasing awareness of environmental matters and the subsequent desire to save resources, recycling would convert an expensive waste disposal into a profitable reusable material. In this study, efforts were made in order to recycle grinded GFRP waste, proceeding from pultrusion production scrap, into new and sustainable composite materials. For this purpose, GFRP waste recyclates, were incorporated into polyester based mortars as fine aggregate and filler replacements at different load contents and particle size distributions. Potential recycling solution was assessed by mechanical behaviour of resultant GFRP waste modified polymer mortars. Results revealed that GFRP waste filled polymer mortars present improved flexural and compressive behaviour over unmodified polyester based mortars, thus indicating the feasibility of the GFRP industrial waste reuse into concrete-polymer composite materials.

Re-Use Assessment of Thermoset Composite Wastes as Aggregate and Filler Replacement for Concrete-Polymer Composite Materials: A case study regarding GFRP pultrusion wastes

Glass fibre-reinforced plastics (GFRP), nowadays commonly used in the construction, transportation and automobile sectors, have been considered inherently difficult to recycle due to both the cross-linked nature of thermoset resins, which cannot be remoulded, and the complex composition of the composite itself, which includes glass fibres, polymer matrix and different types of inorganic fillers. Hence, to date, most of the thermoset based GFRP waste is being incinerated or landfilled leading to negative environmental impacts and additional costs to producers and suppliers. With an increasing awareness of environmental matters and the subsequent desire to save resources, recycling would convert an expensive waste disposal into a profitable reusable material. In this study, the effect of the incorporation of mechanically recycled GFRP pultrusion wastes on flexural and compressive behaviour of polyester polymer mortars (PM) was assessed. For this purpose, different contents of GFRP recyclates (0%, 4%, 8% and 12%, w/w), with distinct size grades (coarse fibrous mixture and fine powdered mixture), were incorporated into polyester PM as sand aggregates and filler replacements. The effect of the incorporation of a silane coupling agent was also assessed. Experimental results revealed that GFRP waste filled polymer mortars show improved mechanical behaviour over unmodified polyester based mortars, thus indicating the feasibility of GFRP waste reuse as raw material in concrete-polymer composites.

Production of bacterial biopolymers from industrial fat-containing wastes

Dissertation presented in partial fulfilment of the Requirements for the Degree of Master in Biotechnology