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In recent decades, the presence of micropollutants in the environment has been extensively studied due to their high frequency of occurrence, persistence and possible adverse effects to exposed organisms. Concerning chiral micropollutants in the environment, enantiomers are frequently ignored and enantiomeric composition often neglected. However, enantioselective toxicity is well recognized, highlighting the need to include enantioselectivity in environmental risk assessment. Additionally, the information about enantiomeric fraction (EF) is crucial since it gives insights about: (i) environmental fate (i.e., occurrence, distribution, removal processes and (bio)degradation); (ii) illicit discharges; (iii) consumption pattern (e.g., illicit drugs, pharmaceuticals used as recreational drugs, illicit use of pesticides); and (iv) enantioselective toxicological effects. Thus, the purpose of this paper is to provide a comprehensive review about the enantioselective occurrence of chiral bioactive compounds in aquatic environmental matrices. These include pharmaceuticals, illicit drugs, pesticides, polychlorinated biphenyls (PCBs) and polycyclic musks (PCMs). Most frequently analytical methods used for separation of enantiomers were liquid chromatography and gas chromatography methodologies using both indirect (enantiomerically pure derivatizing reagents) and direct methods (chiral stationary phases). The occurrence of these chiral micropollutants in the environment is reviewed and future challenges are outlined. © 2017 by the authors. This work was developed at Laboratory of Environmental Research area/Environmental and Applied Chemistry research line of the IINFACTS-CESPU. The authors acknowledge the financial support from PARMADRUGS-CESPU-2014 and ChiralDrugs_CESPU_2017. This research was partially supported through national funds provided by FCT/MCTES: Foundation for Science and Technology from the Minister of Science, Technology and Higher Education (PIDDAC) and European Regional Development Fund (ERDF) through the COMPETE: Programa Operacional Factores de Competitividade (POFC) programme, under the Strategic Funding UID/Multi/04423/2013, in the framework of the programme PT2020. ARR and MSM acknowledge Fundação para a Ciência e Tecnologia (FCT) for their grants, SFRH/BD/86939/2012 and SFRH/BPD/101703/2014, respectively

In January 2017, the International Seabed Authority released a discussion paper on the development of Environmental Regulations for deep-sea mining (DSM) within the Area Beyond National Jurisdiction (the “Area”). With the release of this paper, the prospect for commercial mining in the Area within the next decade has become very real. Moreover, within nations’ Exclusive Economic Zones, the exploitation of deep-sea mineral ore resources could take place on very much shorter time scales and, indeed, may have already started. However, potentially toxic metal mixtures may be released at sea during different stages of the mining process and in different physical phases (dissolved or particulate). As toxicants, metals can disrupt organism physiology and performance, and therefore may impact whole populations, leading to ecosystem scale effects. A challenge to the prediction of toxicity is that deep-sea ore deposits include complex mixtures of minerals, including potentially toxic metals such as copper, cadmium, zinc, and lead, as well as rare earth elements. Whereas the individual toxicity of some of these dissolved metals has been established in laboratory studies, the complex and variable mineral composition of seabed resources makes the a priori prediction of the toxic risk of DSM extremely challenging. Furthermore, although extensive data quantify the toxicity of metals in solution in shallow-water organisms, these may not be representative of the toxicity in deep-sea organisms, which may differ biochemically and physiologically and which will experience those toxicants under conditions of low temperature, high hydrostatic pressure, and potentially altered pH. In this synthesis, we present a summation of recent advances in our understanding of the potential toxic impacts of metal exposure to deep-sea meio- to megafauna at low temperature and high pressure, and consider the limitation of deriving lethal limits based on the paradigm of exposure to single metals in solution. We consider the potential for long-term and farfield impacts to key benthic invertebrates, including the very real prospect of sub-lethal impacts and behavioral perturbation of exposed species. In conclusion, we advocate the adoption of an existing practical framework for characterizing bulk resource toxicity in advance of exploitation. info:eu-repo/semantics/publishedVersion

Sediments in the Nazare Canyon (NE Atlantic) are inhabited by unexpectedly high abundances of the deposit-feeding holothurian Molpadia musculus. The energetic demand of such a large megafaunal biomass is presumably high and requires the efficient exploitation of the food inputs coming from the photic zone. We hypothesise the existence of cooperative interactions between these deep-sea holothurians and prokaryotes in their guts. To investigate these interactions, sediment samples and holothurians were collected at ca. 3500 m depth using a Remote Operated Vehicle (ROV) and an incubation chamber used to "harvest" faeces from the holothurian. In all of these samples (ingested sediment from different sectors of the holothurian gut content, faeces and sediments) we determined total prokaryotic abundance, the relative abundance of Bacteria and Archaea (by means of Catalysed Reporter Deposition-Fluorescence in situ Hybridisation) and bacterial diversity (by means of fingerprinting techniques: ARISA and T-RFLP). Prokaryotic abundances and bacterial diversity in the holothurian gut were very high (up to 10(5) bacterial Operational Taxonomic Units) and significantly greater than in surrounding bottom sediments. Archaea represented a key component within the gut of the holothurians and in certain tracts dominated the prokaryotic assemblage. We also found that ca. 40% of bacterial OTUs were associated uniquely with the gut contents (i.e., absent in surrounding sediments). These findings suggest the occurrence of wide and highly diversified interactions between prokaryotes and deep-sea holothurians. Results presented here provide new insights into the potential relationships between deep-sea holothurians and specific associations of Archaea and Bacteria within their guts. The work opens new perspectives for investigating the diversity of prokaryotes associated to deep-sea megafauna. (C) 2012 Elsevier Ltd. All rights reserved.

Significantly overrepresented Biological Process GO terms identified for the head transcriptome (FDR 

Volcanic archipelagos are a source of numerous on- and offshore geohazards, including explosive eruptions and potentially tsunamigenic large-scale flank collapses. Fogo Island in the southern Cape Verdes is one of the most active volcanoes in the world, making it both prone to collapse (as evidenced by the c. 73 ka Monte Amarelo volcanic flank collapse), and a source of widely distributed tephra and volcanic material. The offshore distribution of the Monte Amarelo debris avalanche deposits and the surrounding volcaniclastic apron were previously mapped using only medium-resolution bathymetric data. Here, using recently acquired, higher-resolution acoustic data, we revisit Fogo's flank collapse and find evidence suggesting that the deposition of hummocky volcanic debris originating from the failed eastern flank most likely triggered the contemporaneous, multi-phase failure of pre-existing seafloor sediments. Additionally, we identify, for the first time, multiple mass-transport deposits in the southern part of the volcaniclastic apron of Fogo and Santiago based on the presence of acoustically chaotic deposits in parametric echo sounder data and volcaniclastic turbiditic sands in recovered cores. These preliminary findings indicate a long and complex history of instability on the southern slopes of Fogo and suggest that Fogo may have experienced multiple flank collapses.

In recent decades, the occurrence of pharmaceuticals in the environment has been widely reported due to their high frequency and recalcitrance in many cases. Concerning the chiral pharmaceuticals (CPs) in environmental matrices, the stereochemistry is often neglected and enantiomers are determined together as unique molecules. However, it is well known that CPs might have enantioselective toxicity, rendering important to assess the occurrence and degradation processes of single enantiomers in the environment, namely during biological treatment in wastewater treatment plants (WWTPs). The development of analytical methods to qualitatively and quantitatively evaluate the enantiomers of CPs is crucial for determining enantiomeric fraction (EF). The EF is the most important parameter in studies involving enantiomers and enantioselective processes and fundamental in biodegradation studies and wastewater monitoring. This review summarizes the analytical methods used to determine EF of CPs in environmental matrices and/or during biodegradation processes. The occurrence of CPs in the environment and their biodegradation are reviewed and future trends in the area outlined.

This work was supported through national funds provided by FCT/MCTES - Foundation for Science and Technology from the Minister of Science, Technology and Higher Education (PIDDAC) and European Regional Development Fund (ERDF) through the COMPETE - Programa Operacional Factores de Competitividade (POFC) programme, under the projects PTDC/MAR-BIO/4694/2014 (reference POCI-01-0145-FEDER-016790; Project 3599 - Promover a ProducAo Cientifica e Desenvolvimento Tecnologico e a ConstituicAo de Redes Tematicas (3599-PPCDT)) and PTDC/SAU-PUB/28736/2017 (reference POCI-01-0145-FEDER- 028736) in the framework of the programme PT2020. D. R. P. L. is grateful for research grant PTDC/MAR-BIO/4694/2014-BI-2017-003. J. X. S. thanks the FCT PhD Programmes and Programa Operacional Capital Humano (POCH), specifically the BiotechHealth Programme (Doctoral Programme on Cellular and Molecular Biotechnology Applied to Health Sciences), reference PD/00016/2012; through the FCT and POCH for PhD grants (SFRH/BD/98105/2013 and SFRH/BD/116167/2016). The authors would like to thank Sara Cravo and Gisela Adriano for the technical support, the Centro de Apoio Cientifico e Tecnoloxico a Investigation (C.A.C.T.I., University of Vigo, Pontevedra, Spain) for HRMS analysis, the Centro de Materiais da Universidade do Porto (CEMUP, Porto, Portugal) for HRMS, and the Departamento de Quimica da Universidade de Aveiro (Portuguese NMR network) for the NMR analysis. Natural products had always be an important source of new hits and leads in drug discovery. The marine environment has been regarded as a significant souce of novel and exquisite bioactive compounds. Yicathins B and C are two marine derived xanthones that have shown antibacterial and antifungal activities. Herein, the total synthesis of these yicathins is reported for the first time as well as six novel analogues. As marine natural products tend to bear very lipophilic scaffolds, the lipophilicity of yicathins and its analogues was evaluated using the classical octanol:water system and a biomimetic model based system. As the xanthonic nucleus is a â privileged structureâ , other biological activities were evaluated, namely antitumor and anti-inflammatory activities. An interesting anti-inflammatory activity was identified for yicathins analogues that paves the way for the design of dual activity (anti-infective and anti-inflammatory) marine inspired xanthones derivatives.