Remoção de ibuprofeno de águas por oxidação catalítica

A ocorrência e destino de fármacos no ambiente aquático tem vindo a ser reconhecido como um problema emergente em química ambiental. Alguns compostos são resistentes à degradação nas estações de tratamento de águas residuais, ETARs, enquanto que outros, ainda que sofram degradação parcial, continuam a ser lançados nos meios aquáticos em quantidades apreciáveis. O Ibuprofeno, IB, um dos anti­ inflamatórios mais consumidos por todo o mundo, é um dos fármacos mais detectados no meio hídrico. Apesar dos sistemas de tratamento convencionais utilizados nas ETARs removerem até 90% do IB das águas residuais, é frequente o efluente descarregado conter ainda quantidades significativas deste poluente. A presença destes compostos no ambiente deve ser avaliada dado que possuem actividade biológica, mesmo a baixas concentrações. Os processos avançados de oxidação com peróxido de hidrogénio, na presença de catalisadores heterogéneos, permitem melhorar significativamente a remoção deste tipo de compostos em águas. Assim, foi objectivo deste trabalho o estudo da utilização de peróxido de hidrogénio como agente oxidante na remoção de IB em soluções aquosas, na presença de complexo de acetilacetonato de Ni (II) disperso em PDMS ou encapsulado em zeólitos NaY. Para o doseamento do fármaco em solução foi necessário desenvolver um método analítico consistindo de separação cromatográfica por HPLC e detecção e quantificação por UV-Vis. Não houve necessidade de recorrer a um passo de pré­ concentração de amostras por extracção em fase sólida (SPE) devido ao facto das concentrações de IB medidas ao longo do trabalho se terem sempre encontrado acima do LOQ (811 g L-1) do método analítico por injecção directa. Deste estudo pode concluir-se que o catalisador que apresentou melhor actividade catalítica e consequentemente maior remoção do IB em solução, foi o complexo de acetilacetonato de Ni (II), disperso em PDMS. Foi avaliada a influência, na conversão do IB, de diferentes parâmetros como a concentração inicial de peróxido de hidrogénio adicionada, quantidade de catalisador utilizada na mistura reaccional e temperatura. Os resultados permitiram concluir que os aumentos destes parâmetros conduzem a um aumento da actividade catalítica da reacção. A estabilidade catalítica do acetilacetonato de Ni (II)/PDMS, foi avaliada em ensaios consecutivos com a mesma amostra e nas mesmas condições, tendo-se observado que, após 8 utilizações, o catalisador perde ligeiramente a actividade (cerca de 11% do seu valor inicial). ABSTRACT: The presence and fate of pharmaceuticals in the aquatic environment is an emergent issue in environmental chemistry. Some compounds are poorly removed in wastewater treatment plants (WWTPs) while others, in spite of being partially removed, are still present in the WWTPs effluents and discharged in the receiving water bodies. Ibuprofen, IB, a non-steroid anti-inflammatory drug, is one of the most used and also one of the most frequently detected pharmaceutical contaminants in aquifers worldwide. Its removal by conventional wastewater treatment processes used in most WWTPs is usually high (up to 90% of incoming IB may be removed), but duet the high loads present in the influents, still significant amounts of IB usually leave the WWTPs in the treated effluents. The presence of these compounds in the environment must be evaluated considering that they may have some biological activity even at low concentrations. Advanced oxidation processes using hydrogen peroxide, in the presence of heterogeneous catalysts, provide a significantly improved removal of this type of substances from waters. Therefore, it was the aim of this work to study the use of hydrogen peroxide as an oxidizing agent in the removal of IB from aqueous solutions, in the presence of the catalyst nickel (II) acetylacetonate dispersed in PDMS or encapsulated in the NaY zeolite. For the quantification of the pharmaceutical in aqueous solution it was necessary to develop an analytical methodology based in chromatographic separation by HPLC and with UV-Vis detection and quantification. There was no need for a pre­concentration step of the samples by solid phase extraction (SPE) as the IB concentrations measured were always above the limit of quantification (811 bL1 of) the analytical method. The results from this study have shown that the catalyst which presented the best catalytic activity and the highest IB removal in solution was nickel (II) acetylacetonate dispersed in PDMS.

Caracterização biogeoquímica de minas abandonadas: os casos da mina de São Domingos e da mina da Mostardeira

O objectivo do presente trabalho foi avaliar os impactos ambientais de duas áreas mineiras abandonadas, a Mina de São Domingos e a Mina da Mostardeira. Procedeu-se a uma caracterização biogeoquímica detalhada das duas áreas mineiras e suas envolventes, a qual consistiu na análise de parâmetros físico-químicos e determinação das concentrações de metais nos aquíferos adjacentes; identificação da flora nativa; caracterização mineralógica dos resíduos mineiros, escórias, solos e sedimentos; e avaliação dos seus prováveis perigos ambientais através da determinação dos teores total, parcial e lixiviável de metais presentes. Os resultados permitiram aprofundar o conhecimento dos processos que ocorrem nestes sistemas e as plantas nativas que colonizam os solos metalíferos da mina de São Domingos foram estudadas não só para avaliar o seu potencial como hiperacumuladoras mas também para estudar em detalhe os mecanismos de tolerância e defesa apresentados pelas plantas desenvolvidas sob stress metálico e o trinómio solo-metal-planta. ABSTRACT: The purpose of this study was to evaluate the environmental impacts of two old mining areas, the São Domingos Mine and the Mostardeira Mine. A detailed biogeochemical characterization of the two mining areas and their surroundings was performed including the analysis of physical and chemical parameters and the determination of metal concentrations in adjacent aquifers, identification of native flora, study of the mineralogy of the tailings, slags, soils and sediments, and assessment of their likely environmental hazards by determining the levels of total, partial and leachable metals present. The results led to a greater understanding of the geochemical processes occurring in these systems. Furthermore, the study of the native plants that colonize the metalliferous soils of São Domingos mine allowed a deeper insight on the mechanisms of tolerance and defense developed by plants under metallic stress and also to evaluate their hyper accumulator potential and therefore their potential use in phytoremediation strategies.

Large scale underground energy storage for renewables integration: general criteria for reservoir identification and viable technologies.

The increasing integration of renewable energies in the electricity grid contributes considerably to achieve the European Union goals on energy and Greenhouse Gases (GHG) emissions reduction. However, it also brings problems to grid management. Large scale energy storage can provide the means for a better integration of the renewable energy sources, for balancing supply and demand, to increase energy security, to enhance a better management of the grid and also to converge towards a low carbon economy. Geological formations have the potential to store large volumes of fluids with minimal impact to environment and society. One of the ways to ensure a large scale energy storage is to use the storage capacity in geological reservoir. In fact, there are several viable technologies for underground energy storage, as well as several types of underground reservoirs that can be considered. The geological energy storage technologies considered in this research were: Underground Gas Storage (UGS), Hydrogen Storage (HS), Compressed Air Energy Storage (CAES), Underground Pumped Hydro Storage (UPHS) and Thermal Energy Storage (TES). For these different types of underground energy storage technologies there are several types of geological reservoirs that can be suitable, namely: depleted hydrocarbon reservoirs, aquifers, salt formations and caverns, engineered rock caverns and abandoned mines. Specific site screening criteria are applicable to each of these reservoir types and technologies, which determines the viability of the reservoir itself, and of the technology for any particular site. This paper presents a review of the criteria applied in the scope of the Portuguese contribution to the EU funded project ESTMAP – Energy Storage Mapping and Planning.

Métodos tradicionais de sondagem e construção de captação de água subterrânea em países em vias de desenvolvimento

Neste trabalho avaliam-se e comparam-se metodologias tradicionais de prospeção e construção de captações de água subterrânea em países em vias de desenvolvimento, neste caso do Sul da Ásia (Butão, Bangladeche, Índia, Nepal e Paquistão). Faz-se uma análise às metodologias do ponto de vista geológico (diversos tipos de aquífero, litologias, graus de fracturação e alteração), mecânico (técnica das metodologias de perfuração e construção das captações), e económico (comparação dos tempos de avanço das sondagens, dos tempos de construção das captações, da produtividade das mesmas e seus custos). Conclui-se que as metodologias de prospeção low cost e tradicionais são semelhantes em âmbito e em cenário de aplicação, e que, ainda que as segundas sejam mais caras, têm custos muito menores em comparação com as convencionais. Conclui-se ainda que as metodologias convencionais de construção de captações estão pensadas para metodologias convencionais de prospeção, e que as low cost são muito semelhantes entre si; Abstract: The present work evaluates and compares traditional methods of borehole drilling and construction for water abstraction in developing countries, particularly South Asia (Bhutan, Bangladesh, India, Nepal and Pakistan). The methods are analyzed in regards to geology (types of aquifers, lithologies, massif fractures and weathering), mechanic (borehole drilling and abstraction technologies), and economic (comparing the progression in drilling and construction of boreholes, productivity and its costs) factors. It is concluded that the traditional drilling methods are similar in scope and application set, and that, though the latter are more expensive, they cost less than conventional methods. It is also concluded that conventional borehole construction is based in conventional drilling methods, and that the diverse low cost methodologies are very similar between them.

PREVENCIÓN Y RESOLUCIÓN DE POTENCIALES CONFLICTOS SOCIOAMBIENTALES EN LA CUENCA DEL RÍO TÉRRABA: EL CASO DEL PROYECTO HIDROELÉCTRICO BORUCA

La microcuenca del río Poás (ubicada entre el volcán Barva y el volcán Poás, hasta la confluencia con el río Grande cerca de la ciudad de Alajuela) posee un alto potencial para la formación de acuíferos de alta calidad. Por este motivo sus recursos naturales deben utilizarse adecuadamente. La mejor manera de lograr lo anterior es mediante la planificación del uso de la tierra. En esta investigación se plantea para ello el ordenamiento territorial y el manejo de cuencas. Para este propósito se realiza una zonificación mediante la cual se identifican las siguientes zonas: sin restricción de uso, uso restringido y uso muy restringido. La mayor parte de la m icrocuenca (64,6%) se encuentra en la categoría de “sin restricción de uso”. Sin embargo. se hace necesaria la intervención con rapidez en sectores ubicados en la parte alta de la microcuenca que se clasifican de “uso muy restringido”. En relación con el recurso hídrico, en la microcuenca en los últimos 14 años y de acuerdo con la metodología aplicada, se ha elevado la producción hídrica, específicamente en la escorrentía y la ganancia. En general aumentó en 1,6%.Abstract:The Poas river micro watershed (located between the Barva and Poas volcanoes reaching the confluence of the Grande river near the city of Alajuela) has high potential for developing high quality aquifers, thus, its natural resnurces should be utilized adequately. This is best done by proper land use planning. In this study guidelines are presented for land use planning and watershed management. Land use is zoned or classified for the following uses:unrestricted use, restricted use, and highly restricted use. Most of the micro watershed (64.6 percent) is classified or zoned as ‘unrestricted use.’ However, urgent intervention is needed in demand and the possibility to export it. However, it is also possible to see the negative impaci of the project, such as: indigenous territories and a pan of the Interamerican Road being flooding, population displacement and the environmental ¡mpact on the Terraba-Sierpe mangrove. This diversity and incompatibility of factors and interest make a complex scenario that potentializes diverse conflicts.

MANEJO Y ORDENAMIENTO TERRITORIAL DE CUENCAS DE COSTA RICA. EL CASO DE LA MIÇROCUENCA DEL RÍO POÁS

La microcuenca del río Poás (ubicada entre el volcán Barva y el volcán Poás, hasta la confluencia con el río Grande cerca de la ciudad de Alajuela) posee un alto potencial para la formación de acuíferos de alta calidad. Por este motivo sus recursos naturales deben utilizarse adecuadamente. La mejor manera de lograr lo anterior es mediante la planificación del uso de la tierra. En esta investigación se plantea para ello el ordenamiento territorial y el manejo de cuencas. Para este propósito se realiza una zonificación mediante la cual se identifican las siguientes zonas: sin restricción de uso, uso restringido y uso muy restringido. La mayor parte de la microcuenca (64,6%) se encuentra en la categoríade “sin restricción de uso”. Sin embargo. se hace necesaria la intervención con rapidez en sectores ubicados en la parte alta de la microcuenca que se clasifican de “uso muy restringido”. En relación con el recurso hídrico, en la microcuenca en los últimos 14 años y de acuerdo con la metodología aplicada, se ha elevado la producción hídrica, específicamente en la escorrentía y la ganancia. En general aumentó en 1,6%.Abstract: The Poas river micro watershed (located between the Barva and Poas volcanoes reaching the confluence of the Grande river near the city of Alajuela) has high potential for developing high quality aquifers. thus, its natural resources should be utilized adequately. This is best done by proper land use planning. In this study guidelines are presented for land use planning and watershed management. Land use is zoned or classified for the following uses: unrestncted use, restricted use, and highly restricted use. Most of the micro watershed (64.6 percent) is classified or zoned as ‘unrestricted use.’ However, urgent intervention is needed in the upper areas of the micro watershed cla.ssified as ‘highly restricted use.’ In the Iast l4years. according Lo the methodology applied, hydrologic production has increased about 1.6 percent. specifically in runoff and soil moisture surpius.

Double Dyke System - Natural engineering solutions

According to various studies, the effects of climate change will be a danger to ecosystems and the population, especially in coastal areas, increasing the risk of floods. Authorities are taking action to prevent future disasters using traditional engineering solutions. These solutions can have high environmental and economic costs, fixing the coastline, increasing the salinization of aquifers, and can be subject to failure mechanisms. For this reason, studies were made to use natural engineering solutions for coastal protection, instead of traditional solutions, to achieve the UN SDGs. Coastal ecosystems have the natural ability to repair and restore themselves, increasing soil elevation, and attenuating waves. One of these solutions is the Double Dyke System, consisting of creating a salt marsh between the first dyke and a second inland. The goal is to protect the coasts and to restore ecosystems. The purpose of this study is to compare the costs of natural engineering solutions with traditional ones. It is assumed that these solutions may be more effective and less expensive in the long run. For this evaluation, a suitability analysis of the polders in the Dutch Zeeland region to assess the costs and benefits under different SLR scenarios was made. A saline intrusion model was also created to analyze the effects of a salt marsh on the aquifers. From the analyzes conducted, the implementation of the DDS turns out to be the cheapest coastal defense system in all SLR scenarios. The presence of a salt marsh could also have a positive impact on the prevention of saline intrusion in the various scenarios considered. The DDS could have a positive economic and environmental impact in the long term, reducing the investment costs for coastal defense and bringing important benefits for the protection of man and nature. Despite the results, more studies are needed on the efficiency of this defense system and on the economic evaluation of non-marketable ecosystem services.

Coupled wellbore-reservoir simulation of thermal effects during multiphase CO2 injection

T2Well-ECO2M is a coupled wellbore reservoir simulator still under development at Lawrence Berkeley National Laboratory (USA) with the ability to deal with a mixture of H2O-CO2-NaCl and includes the simulation of CO2 phase transition and multiphase flow. The code was originally developed for the simulation of CO2 injection into deep saline aquifers and the modelling of enhanced geothermal systems; however, the focus of this research was to modify and test T2Well-ECO2M to simulate CO2 injection into depleted gas reservoirs. To this end, the original code was properly changed in a few parts and a dedicated injection case was developed to study CO2 phase transition inside of a wellbore and the corresponding thermal effects. In the first scenario, the injection case was run applying the fully numerical approach of wellbore to formation heat exchange calculation. Results were analysed in terms of wellbore pressure and temperature vertical profiles, wellhead and bottomhole conditions, and characteristic reservoir displacement fronts. Special attention was given to the thorough analysis of bottomhole temperature as the critical parameter for hydrate formation. Besides the expected direct effect of wellbore temperature changes on reservoir conditions, the simulation results indicated also the effect of CO2 phase change in the near wellbore zone on BH pressure distribution. To test the implemented software changes, in a second scenario, the same injection case was reproduced using the improved semi-analytical time-convolution approach for wellbore to formation heat exchange calculation. The comparison of the two scenarios showed that the simulation of wellbore and reservoir parameters after one year of continuous CO2 injection are in good agreement with the computation time to solve the time-convolution semi-analytical reduced. The new updated T2Well-ECO2M version has shown to be a robust and performing wellbore-reservoir simulator that can be also used to simulate the CO2 injection into depleted gas reservoirs.

Testing the effectiveness of phytoscreening to monitor shallow groundwater contamination by chlorinated ethenes

The research presented herein aims to investigate the strengths and weaknesses of a relatively new technique called phytoscreening. Parallel to the well-known phytoremediation, it consists of exploiting the absorbing potential of trees to delineate groundwater contamination plumes, especially for chlorinated ethenes (i.e., PCE, TCE, 1,2-cis DCE, and VC). The latter are prevalent contaminants in groundwater but their fate and transport in surface ecosystems, such as trees, are still poorly understood and subjected to high variability. Moreover, the analytical validity of tree-coring is still limited in many countries due to a lack of knowledge of its application opportunities. Tree-cores are extracted from trunks and generally analyzed by gas chromatography/mass spectrometry. A systematic review of former literature on phytoscreening for chlorinated ethenes is presented in this PhD thesis to evaluate the factors influencing the effectiveness of the technique. Besides, we tested the technique by probing eight sites contaminated by chlorinated ethenes in Italy (Emilia-Romagna) in different hydrogeological and seasonal settings. We coupled the technique with the assessment of gaseous-phase concentrations directly on-site, inserting detector tubes or a photoionization detector in the tree-holes left by the coring tool. Finally, we applied rank order statistic analysis on field data along with literature data to assess under which conditions phytoscreening should be applied to either screen or monitor environmental contamination issues. A relatively high correlation exists between tree-core and groundwater concentrations (Spearman’s ρ > 0.6), being higher for compounds with higher sorption, for sites with shallower and thinner aquifers, and when sampling specific tree types with standardized sampling and extraction protocols. These results indicate the opportunities for assessing the occurrence, type, and concentration of solvents directly from the stem of trees. This can reduce the costs of characterization surveys, allowing rapid identification of hotspots and plume direction and thus optimizing the drilling of boreholes.

Analysis of the long-term subsidence in the urban area of Bologna

Land subsidence in urban areas represents a widespread geological hazard and a pressing challenge for modern society. This research focuses on the subsidence process affecting the city of Bologna (Italy). Since the 1960s, Bologna has experienced ground deformation due to aquifers overexploitation that peaked during the 1970s with rates of 10 cm/year. Despite a general reduction in these rates over the subsequent decades, thanks to groundwater regulations policies, recent data underscore a substantial subsidence resurgence. To reconstruct the subsurface stratigraphic architecture of Bologna’s urban area and generate a 3D geological model, a multidisciplinary approach centred on a stratigraphic analysis relying on the lithofacies criterion was adopted. The convergence of the analyses within this framework resulted in partitioning the study area into three geological domains exhibiting unique morphological features and depositional stacking patterns. Subsequently, since long-term data are crucial for a comprehensive understanding of ongoing subsidence, a methodology was developed to generate cumulative ground displacement time series and maps by integrating ground-based and remotely-sensed measurements. While the reconstructed long-term subsidence field consistently aligns with the primary geological variations summarised in the 3D model, the generated cumulative displacement curves systematically match pluriannual trends observed in groundwater level and pumping monitoring data. Lastly, to evaluate the expression of the observed relationships from a geotechnical perspective, a series of one-dimensional subsidence calculations were conducted considering the mechanical properties of the investigated deposits and piezometric data. These analyses provided valuable insight into the overall mechanical behaviour of the existing soils, as well as the post-pumping groundwater level and pore pressure distributions, consistent with field data. The methodological approach employed enables a comprehensive analysis of land subsidence in urban areas, allowing the exploration of individual factors governing the deformation process and their interactions, even within complex stratigraphic and hydrogeological environments such as Bologna’s urban area.