Pollution of alpine ponds and groundwater by de-icing chemicals (Serra da Estrela, Central Portugal)

The ecological and socioeconomic importance of mountains is being increasingly recognised. Such regions provide key ecosystem services, namely, water supply which benefits local as well as lowland human populations. Besides mountain aqui fers and rivers, alpine lakes and ponds are crucial for water resources management but are also important in hydroecological and wildli fe conservation terms. This study aims at comparing the pollution of surface and underground water bodies by de -icing chemicals in a mountain environment. The influence of geological, geomorphological, pedological, climatic and anthropic conditions is taken into account. The study region is the highest part of the Serra da Estrela, a Mediterranean mountain located in Central Portugal. In this area there is a hydrological system which encompasses water-table aquifers and number of alpine ponds of glacial origin situated between 1500 m a.s.l. and the summit (1993 m a.s.l.). In the study area, the alpine ponds and springs were inventoried. Water sampling campaigns were carried out for hydrogeochemical characterisation of alpine ponds. These results were compared with hydrogeochemical data from water springs obtained in previous studies. Concentration of the following analytes were determined- total organic carbon (TOC), metals (Pb, Zn, Fe, Cu, Ni, Cd, Cr, As, Mn), cations (Na+, K+, Ca2+, Mg2+), anions (F-, CI-, NO3-, SO42-), silica (SiO2) and nutrients (N, P). Additionally, parameters such as pH, conductivity, turbidity and alkalinity were also measured. The hydrogeochemistry of ponds and water table aqui fers affected by de-icing chemicals is clearly different from the one showed by non-polluted water bodies, due to the influence of different physical settings as well as to the spatial distribution of the anthropic influence. The pond and aqui fer contamination affects water quality but may also disturb the local highly sensitive aquatic ecosystems.N/

Occurrence of Trihalomethanes in Chlorinated Waters from Different Sources Used for Urban Supply

Trihalomethanes (THMs) are the most common disinfection by-products formed by the reaction of chlorine and/or bromide with organic matter. Total THMs in chlorinated treated water are defined as the sum of the concentrations of chloroform (TCM), bromodichloromethane (BDCM), dibromochloromethane (DBCM), and bromoform (TBM). The monitoring of trihalomethanes in distribution tap water collected in from five regions of Portugal, from North to South, in a total of 33 samples, during spring to summer season, is described. Solid phase microextraction coupled to gas chromatography and electron capture detector methodology was applied to determine whether THMs concentrations in urban water supply systems are is in agreement with European Regulations. It was found a great discrepancy in total THMs concentration values, with concentrations varying from 1.8-97.7 μg/L, although the results were below the European parametric value of 100 μg/L. Regarding the Environmental Protection Agency regulations, however, only 97% of samples fulfilled the established criterion of 80 μg/L. and investigate if the individual compounds trihalomethanes content in was also investigated in order to determine if there is observed distribution tap water follows a common or a different THMs pattern in close geographical areas. In the geographical areas under study, mean values of concentrations measured revealed two different clusters: one including the three groups from the North geographical areas, with samples revealing a similar pattern (TCM>BDCM>DBCM>TBM), and another including the two groups from South with a different THMs pattern (DBCM>BDCM>TCM>TBM). A great degree of variation in the concentrations of THMs in tap water was observed, although the results the total THMs concentrations were below the European parametric value (100 μg/L). Mean results of samples grouped by five geographical areas revealed a similar pattern in samples collected from North and Centre TCM>BDCM>DBCM>TBM, whereas samples from South presented a different pattern, DBCM>BDCM>TCM>TBM. The origin of raw water (surface or groundwater) seems to influence this different pattern formation of brominated compounds.This work received financial support from the European Union (FEDER funds POCI/01/0145/FEDER/007265) and National Funds (FCT/MEC, Fundação para a Ciência e Tecnologia and Ministério da Educação e Ciência) under the Partnership Agreement PT2020 UID/QUI/50006/2013. One of the authors (A. Melo) wishes to thank the Fundação Ciência Tecnologia grant SFRH/BPD/86898/2012.info:eu-repo/semantics/publishedVersio

Estudos de partição e localização de fármacos em lipossomas por técnicas espectroscópicas

Dissertação de Doutoramento em Química apresentada à Faculdade de Ciências da Universidade do Port

Study of rare familial monogenic dyslipidemias

A dislipidemia é um distúrbio do perfil lipídico, seja por elevação ou diminuição de partículas lipídicas. O objetivo deste trabalho é fazer uma revisão dos casos com dislipidemia rara em estudo no Instituto Nacional de Saúde Doutor Ricardo Jorge, apresentando os dados clínicos e moleculares mais relevantes. O perfil lipídico foi determinado para cada caso índex e familiares e o estudo molecular dos genes envolvidos foi realizado por amplificação por PCR e sequenciação de Sanger. Foram estudados, ou está em curso o estudo, de 14 casos índex com os seguintes diagnósticos clínicos: Deficiência familiar em lipoproteína lípase (3), Lipodistrofia familiar parcial de Dunningan Tipo 2 (1), Deficiência em lípase ácida lisossomal (3), Abeta/hipobetalipoproteinemia (2), Deficiência em HDL (1), Hipertrigliceridemia autossómica recessiva (3), Sitosterolemia (1). O fenótipo clínico de cada caso índex é variável dependendo de cada condição. Foi encontrada a causa genética da doença em 8/14 doentes, estando os restantes ainda em estudo. Doentes com as várias dislipidemias raras apresentadas têm um risco acrescido de ter outras doenças graves como pancreatite, doença cardiovascular ou complicações neurológicas e devem, por esta razão, ser identificados o mais precocemente possível, de forma a minimizar ou prevenir os efeitos nefastos destas condições.Dyslipidemia is a disorder of lipid metabolism, characterized by either an increase or decrease in lipid particles. The aim of this study is to review all cases with rare dyslipidemia, studied in the National Health Institute of Portugal, presenting the most relevant clinical and molecular data. Lipid profile was determined for each index case and relatives, and molecular analysis of the genes involved was performed by PCR amplification and Sanger sequencing. This study includes 14 index cases, with the following clinical diagnoses: Familial lipoprotein lipase deficiency (3), Familial partial lipodystrophy, Dunningan Type 2 (1), Lysosomal acid lipase deficiency (3), Abeta / hypobetalipoproteinemia (2), HDL deficiency (1), Autosomal recessive hypertriglyceridemia (3), Sitosterolaemia (1). The clinical phenotype of each index case varies depending on each condition. It was possible to find the genetic cause of the disease in 8/14 patients, and the remaining are still under study. Patients with the rare dyslipidemias presented have an increased risk of having other serious disorders such as pancreatitis, cardiovascular disease or neurological complications and should, therefore, be identified as early as possible in order to minimize or prevent the adverse effects of these conditions

Occurrence of persistent organic pollutants at Alqueva's surface water at touristic spots

Freshwater pollution is a huge concern. A study aiming to evaluate water quality and occurence of two groups of persistent environmental pollutants with similar chemical properties (polycyclic aromatic hydrocarbons-PAHs and microplastics -MPs) in Alqueva’s surface water was performed during 2021. Samples were collected at three spots related to touristic activities (two beaches and one marina) once by season. In addition, we assessed and compared the presence of biofilms on plastic and natural materials. Water quality was acceptable with a low eutrophication level. PAHs concentration levels were lower than the standard limits established for surface waters. PAHs profiles showed significant differences when comparing the dry and rainy seasons, with a higher number of different compounds detected in Spring. Low molecular weight compounds, usually associated with the atmospheric deposition and petroleum contamination, were more prevalent. MPs were detected in all samples except one during Winter. Eight polymers were detected being polyethylene the most frequent. Plastics were more prone to biofilm colonization than natural materials. In addition, biofilms detected on plastics were more complex with higher microbial diversity and richer in EPS. Among microbiota were identified microorganisms previously linked to plastic and PAHs detoxification suggesting the need for further studies to evaluate the viability of using biofilms as part of a green bioremediation strategy to mitigate water pollution.This project has received funding from the European Union's Horizon 2020 research and innovation programme under grant agreementNo 730872. INSA [2020DSA1756, 2020], Helmholtz- Zentrum Berlin für Materialien und Energie (Proposals No 202-10133-ST/ UR, 2020 and 212-10726-ST/UR, 2021).N/

Assessment of ecotoxicological effects of Fojo coal mine waste elutriate in aquatic species (Douro Coalfield, North Portugal)

Introduction: The exploitation of anthracite A in the Pejão mining complex (Douro Coalfield, North Portugal) resulted in the formation of several coal waste piles without proper environmental control. In 2017, a new pedological zonation emerged in the Fojo area, after the ignition and self-burning of some of the coal waste piles, namely: unburned coal waste (UW); burned coal waste, and a cover layer (BW and CL, respectively); uphill soil (US); mixed burned coal waste (MBW); downhill soil (DS). This study aimed to evaluate the toxic effects of 25 soil elutriates from different pedological materials.Methods:Allivibrio fischeri bioluminescence inhibition assay, Lemna minor growth inhibition assay, and Daphnia magna acute assay were used to assess the toxicity effects. Additionally, total chlorophyll and malondialdehyde (MDA) content and catalase (CAT) activity were also evaluated in L. minor.Results and Discussion: The results obtained from each endpoint demonstrated the extremely heterogeneous nature of soil properties, and the species showed different sensibilities to soil elutriates, however, in general, the species showed the same sensitivity trend (A. fischeri > L. minor > D. magna). The potentially toxic elements (PTE) present in the soil elutriates (e.g., Al, Pb, Cd, Ni, Zn) affected significantly the species understudy. All elutriates revealed toxicity for A. fischeri, while US1 and UW5 were the most toxic for L. minor (growth inhibition and significant alterations in CAT activity) and D. magna (100% mortality). This study highlights the importance of studying soil aqueous phase toxicity since the mobilization and percolation of bioavailable PTE can cause environmental impacts on aquatic ecosystems and biota

Bisphenol A migration from plastic materials: direct insight of ecotoxicity in Daphnia magna

Bisphenol A (BPA) is an endocrine disrupting chemical (EDC) whose migration from food packaging is recognized worldwide. However, the real overall food contamination and related consequences are yet largely unknown. Among humans, children’s exposure to BPA has been emphasized because of the immaturity of their biological systems. The main aim of this study was to assess the reproductive impact of BPA leached from commercially available plastic containers used or related to child nutrition, performing ecotoxicological tests using the biomonitoring species Daphnia magna. Acute and chronic tests, as well as single and multigenerational tests were done. Migration of BPA from several baby bottles and other plastic containers evaluated by GC-MS indicated that a broader range of foodstuff may be contaminated when packed in plastics. Ecotoxicological test results performed using defined concentrations of BPA were in agreement with literature, although a precocious maturity of daphnids was detected at 3.0 mg/L. Curiously, an increased reproductive output (neonates per female) was observed when daphnids were bred in the polycarbonate (PC) containers (145.1±4.3 % to 264.7±3.8 %), both in single as in multigenerational tests, in comparison with the negative control group (100.3±1.6 %). A strong correlated dose-dependent ecotoxicological effect was observed, providing evidence that BPA leached from plastic food packaging materials act as functional estrogen in vivo at very low concentrations. In contrast, neonate production by daphnids cultured in polypropylene and non-PC bottles was slightly but not significantly enhanced (92.5±2.0 % to 118.8±1.8 %). Multigenerational tests also revealed magnification of the adverse effects, not only on fecundity but also on mortality, which represents a worrying trend for organisms that are chronically exposed to xenoestrogens for many generations. Two plausible explanations for the observed results could be given: a non-monotonic dose–response relationship or a mixture toxicity effect

Odorant binding proteins : a biotechnological tool for odour control

The application of an odorant binding protein for odour control and fragrance delayed release from a textile surface was first explored in this work. Pig OBP-1 gene was cloned and expressed in Escherichia coli , and the purified protein was biochemically characterized. The IC50 values(concentrations of competitor that caused a decay of fluorescence to half-maximal intensity) were determined for four distinct fragrances, namely, citronellol, benzyl benzoate,citronellyl valerate and ethyl valerate. The results showed a strong binding of citronellyl valerate,citronellol and benzyl benzoate to the recombinant protein, while ethyl valerate displayed weaker binding. Cationized cotton substrates were coated with porcine odorant binding protein and tested for their capacity to retain citronellol and to mask the smell of cigarette smoke. The immobilized protein delayed the release of citronellol when compared to the untreated cotton. According to a blind evaluation of 30 assessors, the smell of cigarette smoke, trapped onto the fabrics’ surface, was successfully attenuated by porcine odorant binding protein (more than 60 % identified the weakest smell intensity after protein exposure compared to β-cyclodextrin-treated and untreated cotton fabrics). This work demonstrated that porcine odorant binding protein can be an efficient solution to prevent and/orremove unpleasant odours trapped on the large surface of textiles. Its intrinsic properties make odorant binding proteins excellent candidates for controlled release systems which constitute a new application for this class of proteins.This work was co-funded by the European Social Fund through the management authority POPH and FCT. The authors Carla Silva and Teresa Matama would like to acknowledge their post-doctoral fellowships: SFRH/BPD/46515/2008 and SFRH/BPD/47555/2008, respectively

Avaliação da Qualidade de águas subterrâneas: estudo de alguns parâmetros físico-químicos

A água subterrânea é um recurso natural valioso que, enquanto tal, deve ser protegido da deterioração e da poluição química. Essa proteção é particularmente importante no que respeita aos ecossistemas dela dependentes e à sua utilização para o abastecimento de água destinada ao consumo humano1. O sector do abastecimento de água em Portugal é um serviço público essencial e insubstituível com grande impacte no bem-estar geral dos cidadãos, na saúde pública, nas atividades económicas e na proteção do ambiente. Serve atualmente cerca de 94% da população portuguesa2, sendo caracterizado por uma grande diversidade em termos dos modelos de gestão, com uma entrada crescente de operadores e de capital estrangeiro3. Atendendo, no entanto, à atual conjetura económica do país e ao panorama tarifário no setor da água e do saneamento, tem vindo a aumentar o consumo de água subterrânea por parte das populações, principalmente em zonas rurais, que recorrem cada vez com maior frequência a furos e poços, bem como a águas de minas e nascentes, para uso doméstico. De acordo com o estudo “Água e Saneamento em Portugal: o Mercado e os Preços” apresentado em Novembro de 2012 pela APDA, e noticiado no jornal Público de 28/11/2012, nos últimos três anos tem vindo a diminuir o consumo de água comprada às empresas ou serviços de abastecimento. Tal tendência tem sido igualmente verificada nos nossos Laboratórios de análise de águas do Porto e Lisboa, verificando-se um aumento do número de pedidos de análise de águas subterrâneas destinadas a consumo humano por particulares. Têm surgido igualmente, com alguma frequência, amostras de poços e furos de captações ilegais e ainda amostras resultantes da mistura de água não tratada com água da rede pública. Torna-se portanto essencial avaliar a potabilidade destas águas, preferencialmente através de análises regulares, uma vez que, mesmo sem sinais visíveis de contaminação a água pode estar poluída, em especial se entre os locais de captação e consumo existem zonas agrícolas, industrializadas ou com fossas séticas, constituindo a ausência de controlo um problema real, capaz de gerar situações muito complexas de saúde pública. Em termos Regulamentares, a qualidade da água para consumo humano segue o disposto no Decreto-Lei n.º 306/2007 de 27 de Agosto, que tem por objetivo proteger a saúde humana dos efeitos nocivos resultantes da eventual contaminação da água e assegurar a disponibilização tendencialmente universal de água salubre, limpa e desejavelmente equilibrada. No respeitante à água subterrânea, o Decreto-Lei n.º 208/2008 de 28 de Outubro estabelece o regime de proteção das águas subterrâneas contra a poluição e deterioração, transpondo para a ordem jurídica interna a Diretiva n.º 2006/118/CE, do Parlamento Europeu e do Conselho, de 12 de Dezembro, relativa à proteção da água subterrânea contra a poluição e deterioração, e regulamenta o artigo 47.º da Lei n.º 58/2005, de 29 de Dezembro (Lei da Água) referente à avaliação do estado químico da água subterrânea. Refere este Decreto que tendo em conta a necessidade de obter níveis de proteção da água subterrânea, dever-se-ão cumprir os critérios já fixados para 2 poluentes (nitratos e pesticidas) e estabelecer normas de qualidade e limiares para um conjunto de outros parâmetros pertinentes (poluentes, grupos de poluentes e indicadores de poluição) que contribuem para que as massas de águas subterrâneas corram o risco de não cumprirem os objetivos da Diretiva-Quadro da Água4. Neste último caso, o estabelecimento de valores numéricos a nível comunitário não foi considerado uma opção viável, devido à grande variabilidade natural de substâncias presentes nas águas subterrâneas (em função das condições hidrogeológicas, das concentrações de fundo geoquímico, dos trajetos dos poluentes e das interações com diversos compartimentos ambientais), exigindo-se que os Estados-Membros estabeleçam as suas próprias normas de qualidade, tendo em conta os riscos identificados e a lista de poluentes/indicadores constante do anexo II da Diretiva 2006/118/CE5. Da lista mínima de poluentes e dos respetivos indicadores para os quais os Estados-Membros têm de considerar a fixação de limiares constam: (a) Substâncias ou iões, ou indicadores, que podem ocorrer naturalmente ou como resultado de atividades humanas (Arsénio, Cádmio, Chumbo, Mercúrio, Azoto amoniacal, Cloreto, Sulfato); (b) Substâncias sintéticas artificiais (Tricloroetileno; Tetracloroetileno) e (c) Parâmetros indicativos de intrusões salinas ou outras (Condutividade / Cloreto, Sulfato). Alguns países estabeleceram já limiares, tendo fundamentalmente por base os padrões de água potável previstos na Diretiva UE (98/83/CE) ou respetivas normas nacionais.Este trabalho objetivou uma avaliação global da qualidade das águas subterrâneas, rececionadas nos nossos Laboratórios do Porto e Lisboa entre os anos de 2010 e 2012, no que respeita a alguns dos poluentes/indicadores referidos (nitratos, sulfatos, cloretos, azoto amoniacal, condutividade e pH) e sua adequação para fins domésticos. Foram analisadas um total de 1518 amostras provenientes de 17 distritos do País, e realizados estudos comparativos referentes a variações geográficas e sazonais

Dispersive Liquid–Liquid Microextraction for the Simultaneous Determination of Parent and Nitrated Polycyclic Aromatic Hydrocarbons in Water Samples

A new method for simultaneous extraction and quantification of 6 nitrated polycyclic aromatic hydrocarbons (nitro-PAHs) and 16 parent polycyclic aromatic hydrocarbons (PAHs) in water matrices was optimized and validated. The extraction procedure was based on dispersive liquid-liquid microextraction technique, followed by gas chromatography-mass detection. The optimum conditions of extraction (volume of the extraction solvent, dispersive solvents and amount of salt) were selected using central composite design. The best results were found by using 200 μL of acetonitrile as dispersive solvent, 60 μL of chloroform as extraction solvent, and 10% (w/v) NaCl. Excellent linearity was observed in the range of 10–150 ng L−1 with correlation coefficients (r2) ranging between 0.9996 and 0.9999 for nitro-PAHs and in the range of 5–150 ng L−1 with r2 ranging from 0.9998 to 1.000 for PAHs. The limits of detection for the nitro-PAHs studied ranged from 0.82 to 3.37 ng L−1, whereas for PAHs ranged from 0.62 to 3.48 ng L−1. The intra- and inter-day precisions for nitro-PAHs were in the range of 0.45 to 19.54% and 0.43 to 19.62%, respectively, and for PAHs ranged between 0.45 to 17.42% and 0.38 to 18.97%, respectively. The proposed method was successfully applied in analyses of groundwater, sea, rain water and river water, being appropriate for routine analyses.This work received financial support from the European Union (FEDER funds POCI/01/0145/FEDER/007265) and National Funds (FCT/MEC, Fundação para a Ciência e Tecnologia and Ministério da Educação e Ciência) under the Partnership Agreement PT2020 UID/QUI/50006/2013. One of the authors (A. Melo) wishes to thank the Fundação Ciência Tecnologia, grant SFRH/BPD/86898/2012.info:eu-repo/semantics/publishedVersio