Caracterización química y mineral ógica de los sedimentos de los canales de Mira, Ílhavo y Ovar de la Laguna de Aveiro (Portugal)

The paleoenvironmental reconstruction of Aveiro Lagoon is being carried out based on the sedimentological, paleoecological, geochemical and mineralogical characterization of sediment samples collected systematically in the lagoon. This paper presents results concerning the changes in the chemical and mineralogical composition of the fine fraction (<63 μm) and the clay fraction (<2 μm) in sediment samples from Aveiro Lagoon, mainly collected from the lower intertidal plain and subtidal deposits located along the Mira, Ílhavo and Ovar channels. A zonography of the lagoon was established based on the parameters analyzed. The results show that the surface and near-surface sediments of Aveiro Lagoon trap relatively large quantities of trace metals, such as Cu, Pb, Co, Ni, Cd, Zn, Fe, Mn and Cr, considered to be partially adsorbed, particularly on silty and clayey particles, and co-precipitated on Fe and Mn oxyhydroxide forms precipitated in the topmost layers of sediments. Series of statistically significant relationships were established between trace metal concentrations and clay content and semi-quantitatively determined clay mineral species in the sediments.La reconstrucción paleoambiental de la Laguna de Aveiro se está realizando mediante la caracterización sedimentológica, paleoecológica, geoquímica y mineralógica de muestras de sedimento recogidas sistemáticamente en la misma. Este artículo presenta resultados relativos a las variaciones en la composición química y mineralógica de las fracciones fina (<63 μm) y arcillosa (<2 μm) de las muestras de sedimento de la Laguna de Aveiro, recogidas principalmente en las planicies intermareales bajas y depósitos submareales de los canales de Mira, Ílhavo y Ovar. Estos parámetros fueron utilizados para caracterizar los sedimentos de cada uno de los canales estudiados de la Laguna de Aveiro. Los sedimentos superficiales y subsuperficiales de esta laguna retienen cantidades relativamente elevadas de elementos vestigiales como Cu, Pb, Co, Ni, Cd, Zn, Fe, Mn y Cr, los cuales se consideran principalmente adsorbidos en partículas fangosas y arcillosas y en óxidos de Fe y Mn. Con base en los parámetros analizados se puede establecer una zonografía de la laguna. Se han encontrado relaciones entre las concentraciones de elementos vestigiales y el contenido de arcilla y las especies minerales de las arcillas en los sedimentos

Expanding the Applicability of Poly(Ionic Liquids) in Solid Phase Microextraction: Pyrrolidinium Coatings

Crosslinked pyrrolidinium-based poly(ionic liquids) (Pyrr-PILs) were synthesized through a fast, simple, and solventless photopolymerization scheme, and tested as solid phase microextraction (SPME) sorbents. A series of Pyrr-PILs bearing three different alkyl side chain lengths with two, eight, and fourteen carbons was prepared, characterized, and homogeneously coated on a steel wire by using a very simple procedure. The resulting coatings showed a high thermal stability, with decomposition temperatures above 350 degrees C, excellent film stability, and lifetime of over 100 injections. The performance of these PIL-based SPME fibers was evaluated using a mixture of eleven organic compounds with different molar volumes and chemical functionalities (alcohols, ketones, and monoterpenes). The Pyrr-PIL fibers were obtained as dense film coatings, with 67 mu m thickness, with an overall sorption increase of 90% and 55% as compared to commercial fibers of Polyacrylate (85 mu m) (PA85) and Polydimethylsiloxane (7 mu m) (PDMS7) coatings, respectively. A urine sample doped with the sample mixture was used to study the matrix effect and establish relative recoveries, which ranged from 60.2% to 104.1%.David J. S. Patinha, and Liliana C. Tome are grateful to FCT (Fundacao para a Ciencia e a Tecnologia) for the PhD research grant SFRH/BD/97042/2013 and the Post-Doctoral research grant (SFRH/BPD/101793/2014), respectively. David J. S. Patinha also thanks the financial support from COST-Exil Project 1206. The NMR data was acquired at CERMAX (Centro de Ressonncia Magnetica Antnio Xavier) which is a member of the National NMR network. This work was partially supported by FCT through Research Unit GREEN-it " Bioresources for Sustainability" (UID/Multi/04551/2013) and the Associate Laboratory CICECO Aveiro Institute of materials (UID/CTM/50011/2013)

Elderberry Stalks as a Source of High-Value Phytochemical: Essential Minerals and Lipophilic Compounds

Elderberry (Sambucus nigra L.) consumption has been growing in the last years, generating a large number of stalks (~10% of the berries bunch) that are still under-valorized. This study focused on the evaluation of elderberry stalks as a source of high-value phytochemicals. In this vein, the essential mineral content and lipophilic composition were analyzed for the first time. In addition, the polar fraction was evaluated regarding its total phenolic content (TPC) and antioxidant activity by both 2,2-azinobis-3-ethylbenzothiazoline-6-sulfonic acid (ABTS) and 2-diphenyl-1-picrylhydrazyl hydrate (DPPH) assays. The lipophilic fraction was mainly composed of triterpenic acids (2902.20 mg kg−1 of dry weight (dw)), fatty acids (711.73 mg kg−1 dw) and sterols (288.56 mg kg−1 dw). Minor amounts of long-chain aliphatic alcohols and other components were also detected. Ursolic acid (2265.83 mg kg−1 dw), hexadecanoic acid (219.85 mg kg−1 dw) and β-sitosterol (202.74 mg kg−1 dw) were the major lipophilic components verified. The results of this study also indicated that elderberry stalks might be used as a natural source of essential minerals, particularly calcium, iron and potassium, which are known to play important roles in various body functions. The analysis of the polar fraction also showed that elderberry stalks present TPC as high as elderberry themselves as well as considerable antioxidant activity (1.04 and 0.37 mmol TE g−1 of extract, against respectively ABTS and DPPH radicals). These results highlight the potential of elderberry stalks as a natural source of high-value phytochemicals that may be explored in several fieldspublishe

Geochemistry, mineralogy, solid-phase fractionation and oral bioaccessibility of lead in urban soils of Lisbon

An urban survey of Lisbon, the largest city in Portugal, was carried out to investigate its environmental burden, emphasizing metallic elements and their public health impacts. This paper examines the geochemistry of lead (Pb) and its influence on human health data. A total of 51 soil samples were collected from urban recreational areas used by children to play outdoors. The semi-quantitative analysis of Pb was carried out by inductively coupled plasma mass spectrometry after an acid digestion. X-ray diffraction was used to characterize the soil mineralogy. The solid-phase distribution of Pb in the urban soils was investigated on a subset of 7 soils, out of a total of 51 samples, using a non-specific sequential extraction method coupled with chemometric analysis. Oral bioaccessibility measurements were obtained using the Unified BARGE Method developed by the Bioaccessibility Research Group of Europe. The objectives of the study are as follows: (1) investigation of Pb solid-phase distribution; (2) interpretation of Pb oral bioaccessibility measurements; (3) integration of metal geochemistry with human health data; and (4) understanding the influence of geochemistry and mineralogy on oral bioaccessibility. The results show that the bioaccessible fraction of Pb is lower when major metal fractions are associated with less soluble soil phases such as Fe oxyhydroxides, and more increased when the metal is in the highly soluble carbonate phase. However, there is some evidence that the proportion of carbonates in the soil environment is also a key control over the oral bioaccessibility of Pb, irrespective of its solid-phase fractionation

URBSOIL-LISBON-Geoquímica dos solos urbanos de Lisboa: caracterização e cartografia, suporte para futuros estudos de saúde humana: resultados preliminares

A Geologia, e em especial a Geoquímica em ambiente urbano, têm-se revelado ferramentas essenciais não só no estudo dos materiais naturais neste ambiente, como na ligação entre a Geologia e a acção antrópica. Este estudo, com uma metodologia que usa vários meios de amostragem, pretende avaliar quais os elementos químicos que podem intervir num contexto de interacção em que as crianças são tomadas como alvo principal. Os primeiros resultados sobre concentrações de elementos químicos para os solos urbanos de Lisboa apontam para uma exposição esparsa na cidade de alguns dos elementos químicos inorgânicos, mas havendo por vezes um zonamento por tipologia de local ou de elemento químico. Foram definidos quatro grupos de pontos de amostragem consoante o tipo de uso, e escolhidos para uma análise mais próxima alguns elementos considerados tendencialmente de input antrópico e que se relacionam com a saúde humana.

High Levels of Heavy Metal(loid)s Related to Biliary Hyperplasia in Hedgehogs (Erinaceus europaeus)

Simple Summary Heavy metal(loid)s are hazardous substances for humans, animals and ecosystems. The liver is one of the most affected organs, presenting lesions after being acutely or chronically exposed to these substances. In this study, hepatic metal(loid)s' concentrations were associated with biliary hyperplasia, which was the most common hepatic lesion found in a group of western-European hedgehogs from rescue centres in Portugal. With exception of arsenic (As), all metal(loid)s were present in higher concentrations in animals with biliary hyperplasia. Further research is necessary to support these results and clarify the molecular mechanisms that lead to hepatic lesions provoked by these compounds. Heavy metal(loid) pollution of ecosystems is a current One Health problem. The liver is one of the most affected organs in cases of acute or chronic exposure to abnormal amounts of these substances, inducing histopathologic lesions. In order to assess the influence of heavy metal(loids), forty-five European hedgehogs (Erinaceus europaeus) were submitted to necropsy, and liver samples were collected for a routine histopathology exam and metal(loid)s determination (As, Cd, Co, Cr, Cu and Pb) by ICP-MS. Age was estimated during the necropsy exam. Biliary hyperplasia was the most frequent lesion observed (16/45; 35.56%). No statistically significant associations were found between biliary hyperplasia and age or sex. Metal(loid)s' concentrations were higher in animals with biliary hyperplasia (except for As). There was a statistically significant difference for both Cd and Co. For As, Cd and Co, cubs and juveniles animals showed significantly lower concentrations than elder individuals. Only for Pb were significant differences found between females and males. As described in the literature, exposure to metal(loid)s may be a cause of biliary hyperplasia, although further research (including the use of biochemical methods) is needed to support these results. To the authors' knowledge, this is the first report of this association in hedgehogs.This work was supported by National Funds by the Portuguese Foundation for Science and Technology (FCT). The authors of the research unit CITAB (CJB and PAO) received funding from FCT-reference of the project: UIDB/04033/2020. The author of the research unit CECAV (FS) received funding from FCT-reference of the project: UIDB/CVT/00772/2020. CJB was supported by FCT due to the phD scholarship 2021.04520.BD. TLM was supported by UIDB/CVT/00772/2020 and LA/P/0059/2020 funded by FCT

Screening polymeric ionic liquids for chromatography-based purification of bacteriophage M13

M13 bacteriophage is a key instrument in phage display applications, as well as a possible antibacterial therapeutic agent due to its highly restrictive bacterial pathogenesis, and other applications. The traditional phage purification process is usually achieved by gradient ultracentrifugation or a combination of precipitation, centrifugation and microfiltration. These approaches easily lead to long process times, high operational costs, phage aggregation and consequent product loss (approximately 60%). This work is thus focused on an alternative potential large-scale process to achieve high yield and purity while minimizing the operational costs. Electrostatic-based separation processes are also common biomolecules purification techniques. Although anion exchange chromatography has been used before to purify several viral particles, this technique has been poorly reported for the purification of M13 phage. In a recent work, our group has demonstrated the use of a predominant anion exchange process, where a polymeric ionic liquid (PIL) was used as an alternative separation matrix for M13 bacteriophage. In this work, a variety of system parameters was studied, including chemical structure of the cation and the anion, the crosslinker nature and its concentration, either in batch adsorption/elution or chromatographic operation mode. The PIL-based chromatographic operation mode revealed to be a suitable separation process for M13 from directly filtered E. coli supernatant, reaching over 70% M13 recovery and 4.6 purification factor in a single step. To our knowledge, this is the first time that PILs have been reported as separation agents for bioproducts from complex mixtures.publishe