Search

Muscleblind-like splicing regulators (MBNLs) are RNA-binding factors that have an important role in developmental processes. Dysfunction of these factors is a key contributor of different neuromuscular degenerative disorders, including Myotonic Dystrophy type 1 (DM1). Since DM1 is a multisystemic disease characterized by symptoms resembling accelerated aging, we asked which cellular processes do MBNLs regulate that make them necessary for normal lifespan. By utilizing the model organism Caenorhabditis elegans, we found that loss of MBL-1 (the sole ortholog of mammalian MBNLs), which is known to be required for normal lifespan, shortens lifespan by decreasing the activity of p38 MAPK/PMK-1 as well as the function of transcription factors ATF-7 and SKN-1. Furthermore, we show that mitochondrial stress caused by the knockdown of mitochondrial electron transport chain components promotes the longevity of mbl-1 mutants in a partially PMK-1-dependent manner. Together, the data establish a mechanism of how DM1-associated loss of muscleblind affects lifespan. Furthermore, this study suggests that mitochondrial stress could alleviate symptoms caused by the dysfunction of muscleblind splicing factor, creating a potential approach to investigate for therapy. [ABSTRACT FROM AUTHOR]

Graphical abstract Highlights • The influence of water matrix on the efficiency of AOTs is overviewed. • Photolysis, photocatalysis, UV/H 2 O 2 -, Fenton-, and O 3 -based processes are reviewed. • Dissolved organic matter and inorganics can act as inhibitors and/or promoters. • The effect results from the interplay of the co-existing substances. • The knowledge on the role of matrix constituents is crucial for installation of AOTs. Abstract Micropollutants (MPs) in the aquatic compartments are originated from many sources and particularly from the effluents of urban wastewater treatment plants (UWWTPs). Advanced oxidation technologies (AOTs) usually applied after biological processes, have recently emerged as effective tertiary treatments for the removal of MPs, but the oxidation rates of the single compounds may be largely affected by the constituent species of the water matrix. These species include dissolved organic matter and inorganic species (e.g., carbonate, bicarbonate, nitrite, sulphate, chloride). This review analyses the impact of such substances on common AOTs including photolysis, UV/H 2 O 2 , Fenton, photocatalysis, and ozone-based processes. The degradation efficiency of single MPs by AOTs results from the combined impact of the water matrix constituents, which can have neutral, inhibiting or promoting effect, depending on the process and the mechanism by which these water components react. Organic species can be either inhibitors (by light attenuation; scavenging effects; or adsorption to catalyst) or promoters (by originating reactive oxygen species (ROS) which enhance indirect photolysis; or by regenerating the catalyst). Inorganic species can also be either inhibitors (by scavenging effects; formation of radicals less active than hydroxyl radicals; iron complexation; adsorption to catalyst or decrease of its effective surface area) or promoters (e.g., nitrate ions by formation of ROS; iron ions as additional source of catalyst). The available data reviewed here is limited and the role and mechanisms of individual water components are still not completely understood. Further studies are needed to elucidate the wide spectrum of reactions occurring in complex wastewaters and to increase the adoption of AOTs in UWWTPs. [ABSTRACT FROM AUTHOR]

Abstract The occurrence of micropollutants in the environment is a matter of high concern. Some regulations have been published in the last years and a Watch List of contaminants of emerging concern (CECs) for European Union monitoring of surface water was launched in the Decision 2015/495, including three estrogens (estrone, E1; 17-β-estradiol, E2; and 17-α-ethinylestradiol, EE2), four pharmaceuticals (diclofenac and the macrolide antibiotics azithromycin, clarithromycin and erythromycin), an anti-oxidant (2,6-ditert-butyl-4-methylphenol, BHT), an UV filter (2-ethylhexyl 4-methoxycinnamate, EHMC), some pesticides (methiocarb and the neonicotinoids imidacloprid, thiacloprid, thiamethoxam, clothianidin and acetamiprid) and two herbicides (oxadiazon and triallate). This study provides the first spatial and seasonal monitoring campaign in the Ave and the Sousa Rivers for the all set of the 17 Watch List CECs (not reported yet for any country), in order to assess their occurrence, distribution, frequency and risk assessment. It also highlights the need of extend the study to other regions and environmental matrices to investigate the occurrence and possible sources of contamination of CECs, aiming to give insights for decision makers to define mitigation strategies for a more sustainable water policy. Graphical abstract Unlabelled Image Highlights • EU Watch List of CECs monitored in the Ave and the Sousa Rivers. • Spatiotemporal monitoring of 2 rivers in 4 seasons: 13 CECs found of a total of 17. • The most frequent CECs were diclofenac, azithromycin and EHMC. • The highest concentrations were verified for diclofenac, EHMC and imidacloprid. • The monitoring of these CECs must be extended to other EU sites. [ABSTRACT FROM AUTHOR]

Abstract The presence of organic micropollutants (MPs) in the aquatic environment is strongly related to their difficult elimination by conventional water and wastewater treatment processes. Therefore, alternative treatment technologies are required to overcome this problem. In this domain, constructed wetlands (CWs) have gained increasing attention in the last years, mainly due to the low-cost, simple operation/maintenance and environmental friendliness of these systems. However, studies on the application of CWs to remove MPs from freshwater aquaculture effluents are still scarce. In this work, planted (Phragmites australis) vertical subsurface flow CWs, at microcosm scale, were investigated for the removal of MPs found in non-spiked freshwater aquaculture effluents, namely atrazine, isoproturon, perfluorooctanesulfonic acid (PFOS), clarithromycin, erythromycin, fluoxetine, norfluoxetine, and 2-ethylhexyl-4-methoxycinnamate (EHMC). A wider multi-component set of 36 MPs was also studied by adding these MPs at 100 ng L−1 to the same matrix (alachlor, atrazine, chlorfenvinphos, isoproturon, PFOS, azithromycin, clarithromycin, erythromycin, diclofenac, methiocarb, acetamiprid, clothianidin, thiacloprid, thiamethoxam, EHMC, simazine, atorvastatin, bezafibrate, carbamazepine, cephalexin, ceftiofur, citalopram, clindamycin, clofibric acid, diphenhydramine, enrofloxacin, fluoxetine, ketoprofen, metoprolol, norfluoxetine, ofloxacin, propranolol, tramadol, trimethoprim, venlafaxine, and warfarin). High weekly removal efficiencies (>87%) were observed for all MPs in both non-spiked and spiked experiments, with the exception of EHMC (removal rates between 0 and 86%). These results emphasize the potential of CWs to remove MPs from freshwater aquaculture effluents, but also the need to enhance the performance of these systems for the elimination of some recalcitrant MPs, such as EHMC, which was found at high concentrations in the studied effluents. Graphical abstract Unlabelled Image Highlights • Constructed wetland microcosms studied for the removal of organic micropollutants. • Spiked (36 micropollutants) and non-spiked aquaculture effluents were investigated. • Most micropollutants found in effluents were removed to below the detection limit. • Weekly removal efficiencies were higher than 87% for most spiked micropollutants. • The UV filter EHMC was the only recalcitrant micropollutant. [ABSTRACT FROM AUTHOR]

Abstract The European Union (EU) has recommended the monitoring of specific priority substances (PSs, Directive 2013/39) and some contaminants of emerging concern (CECs, Decision 2015/495) in surface waterbodies. The present study provides spatial distributions and temporal variations of a wide range of multi-class PSs and CECs in four stressed rivers in Portugal (Ave, Leça, Antuã, and Cértima). Thirteen micropollutants were found in all four rivers, including the priority pesticide isoproturon (up to 92 ng L−1), various pharmaceuticals (up to 396 ng L−1), and the UV-filter 2-ethyl-hexyl-4-methoxycinnamate (EHMC, up to 562 ng L−1) identified in Decision 2015/495. The industrial priority compound perfluorooctanesulfonic acid (PFOS) was found in three rivers (Antuã, Cértima, and Leça) below the method quantification limit, together with four pharmaceuticals not included in these EU guidelines. The already banned priority pesticide atrazine was detected in Ave, Antuã, and Leça (up to 41 ng L−1) and simazine in Cértima and Leça (up to 26 ng L−1). Acetamiprid and imidacloprid (included in Decision 2015/495) were only detected during the dry season in the Ave. Leça river was selected as a waterbody case study for assessment of fluorescence excitation-emission matrices (EEMs). These results matched the spatial distribution trend of micropollutants along the river, with stronger fluorescence response and higher concentrations being found downstream of industrial areas and urban wastewater treatment plants (WWTPs). Moreover, the fluorescence signature of surface water collected downstream of an urban WWTP aligned very well with that obtained for the respective WWTP effluent. Thus, actions are needed to preserve a good environmental status of these stressed European waterbodies. Graphical abstract Unlabelled Image Highlights • Spatial and seasonal variations of multi-class micropollutants were studied. • Four stressed rivers in Portugal were monitored in dry and wet seasons. • Ketoprofen, tramadol, enrofloxacin and thiacloprid were measured at highest levels. • The fluorescence EEMs of surface water matched the distribution of micropollutants. • Correlation of fluorescence signatures found for azithromycin, carbamazepine, EHMC. [ABSTRACT FROM AUTHOR]

Despite the well-documented effect of castration in thymic regeneration, the singular contribution of the bone marrow (BM) versus the thymus to this process remains unclear. The chief role of IL-7 in pre- and intrathymic stages of T lymphopoiesis led us to investigate the impact of disrupting this cytokine during thymic rebound induced by androgen blockade. We found that castration promoted thymopoiesis in young and aged wild-type mice. In contrast, only young germline IL-7-deficient (Il7-/-) mice consistently augmented thymopoiesis after castration. The increase in T cell production was accompanied by the expansion of the sparse medullary thymic epithelial cell and the peripheral T cell compartment in young Il7-/- mice. In contrast to young Il7-/- and wild-type mice, the poor thymic response of aged Il7-/- mice after castration was associated with a defect in the expansion of BM hematopoietic progenitors. These findings suggest that BM-derived T cell precursors contribute to thymic rebound driven by androgen blockade. To assess the role of IL-7 within the thymus, we generated mice with conditional deletion of IL-7 (Il7 conditional knockout [cKO]) in thymic epithelial cells. As expected, Il7cKO mice presented a profound defect in T cell development while maintaining an intact BM hematopoietic compartment across life. Unlike Il7-/- mice, castration promoted the expansion of BM precursors and enhanced thymic activity in Il7cKO mice independently of age. Our findings suggest that the mobilization of BM precursors acts as a prime catalyst of castration-driven thymopoiesis. [ABSTRACT FROM AUTHOR]

The contamination of fresh water is a global concern. The huge impact of natural and anthropogenic organic substances that are constantly released into the environment, demands a better knowledge of the chemical status of Earth’s surface water. Water quality monitoring studies have been performed targeting different substances and/or classes of substances, in different regions of the world, using different types of sampling strategies and campaigns. This review article aims to gather the available dispersed information regarding the occurrence of priority substances (PSs) and contaminants of emerging concern (CECs) that must be monitored in Europe in surface water, according to the European Union Directive 2013/39/EU and the Watch List of Decision 2015/495/EU, respectively. Other specific organic pollutants not considered in these EU documents as substances of high concern, but with reported elevated frequency of detection at high concentrations, are also discussed. The search comprised worldwide publications from 2012, considering at least one of the following criteria: 4 sampling campaigns per year, wet and dry seasons, temporal and/or spatial monitoring of surface (river, estuarine, lake and/or coastal waters) and ground waters. The highest concentrations were found for: (i) the PSs atrazine, alachlor, trifluralin, heptachlor, hexachlorocyclohexane, polycyclic aromatic hydrocarbons and di(2-ethylhexyl)phthalate; (ii) the CECs azithromycin, clarithromycin, erythromycin, diclofenac, 17α-ethinylestradiol, imidacloprid and 2-ethylhexyl 4-methoxycinnamate; and (iii) other unregulated organic compounds (caffeine, naproxen, metolachlor, estriol, dimethoate, terbuthylazine, acetaminophen, ibuprofen, trimethoprim, ciprofloxacin, ketoprofen, atenolol, Bisphenol A, metoprolol, carbofuran, malathion, sulfamethoxazole, carbamazepine and ofloxacin). Most frequent substances as well as those found at highest concentrations in different seasons and regions, together with available risk assessment data, may be useful to identify possible future PS candidates. [ABSTRACT FROM AUTHOR]

The importance of stereochemistry for medicinal chemistry and pharmacology is well recognized and the dissimilar behavior of enantiomers is fully documented. Regarding the environment, the significance is equivalent since enantiomers of chiral organic pollutants can also differ in biodegradation processes and fate, as well as in ecotoxicity. This review comprises designed biodegradation studies of several chiral drugs and pesticides followed by enantioselective analytical methodologies to accurately measure the enantiomeric fraction (EF). The enantioselective monitoring of microcosms and laboratory-scale experiments with different environmental matrices is herein reported. Thus, this review focuses on the importance of evaluating the EF variation during biodegradation studies of chiral pharmaceuticals, drugs of abuse, and agrochemicals and has implications for the understanding of the environmental fate of chiral pollutants. [ABSTRACT FROM AUTHOR]

Thymic epithelial cells (TECs) provide crucial microenvironments for T-cell development and tolerance induction. As the regular function of the thymus declines with age, it is of fundamental and clinical relevance to decipher new determinants that control TEC homeostasis in vivo. Beyond its recognized tumor suppressive function, p53 controls several immunoregulatory pathways. To study the cell-autonomous role of p53 in thymic epithelium functioning, we developed and analyzed mice with conditional inactivation of Trp53 in TECs (p53cKO). We report that loss of p53 primarily disrupts the integrity of medullary TEC (mTEC) niche, a defect that spreads to the adult cortical TEC compartment. Mechanistically, we found that p53 controls specific and broad programs of mTEC differentiation. Apart from restraining the expression and responsiveness of the receptor activator of NF-κB (RANK), which is central for mTEC differentiation, deficiency of p53 in TECs altered multiple functional modules of the mTEC transcriptome, including tissue-restricted antigen expression. As a result, p53cKO mice presented premature defects in mTEC-dependent regulatory T-cell differentiation and thymocyte maturation, which progressed to a failure in regular and regenerative thymopoiesis and peripheral T-cell homeostasis in the adulthood. Lastly, peripheral signs of altered immunological tolerance unfold in mutant mice and in immunodeficient mice that received p53cKO-derived thymocytes. Our findings position p53 as a novel molecular determinant of thymic epithelium function throughout life. [ABSTRACT FROM AUTHOR]

The fate and removal of organic micropollutants in the environment is a demanding issue evidenced by the recent European policy. This work presents an analytical method for the trace quantification of 37 micropollutants including Priority Substances (Directive 2013/39/EU), substances of the recent watch list (Decision 2015/495/EU) and contaminants of emerging concern: pesticides, multi-class pharmaceuticals and a metabolite, estrogens and one industrial compound. The analytical method was based on solid phase extraction (SPE) followed by ultra-high performance liquid chromatography with tandem mass spectrometry (UHPLC–MS/MS), using eco-friendly solvents (ethanol and ultrapure water) both in the SPE and UHPLC, according to green analytical chemistry principles. Briefly, Oasis ® HLB cartridges were used to preconcentrate 100 mL of water samples and the reconstituted extracts were analyzed with a Kinetex™ column under reversed mode, the linear ranges extended to 200 ng L −1 ( R 2 > 0.99) for all the analytes. The method detection limits were between 0.04 and 2.26 ng L −1 and the method quantification limits were between 0.13 and 6.85 ng L −1 . The identity of the compounds was confirmed using two MS/MS transitions and its ion ratios, according to Decision 2002/657/EC. The validated method was applied to wastewater treatment plant samples, assessing the concentration of micropollutants after secondary biological and tertiary UV treatments. Lab-scale photolysis and ozonation experiments were also performed with the secondary effluents, with ozonation showing the best performance for the removal of most of the determined micropollutants. [ABSTRACT FROM AUTHOR]

• Ozonation investigated for the removal of antibiotics from aquaculture effluents. • Oxytetracycline, sulfamethoxazole and trimethoprim attacked by O 3 directly. • Florfenicol removed by hydroxyl radicals (HO•) only. • Sulfadimethoxine degradation is significantly affected by the water matrix. • Toxicological evaluation did not show increase of water toxicity after ozonation. Antibiotics are often applied in aquaculture to prevent fish diseases. These substances can cause disturbances on receiving waters, when not properly eliminated from the aquaculture effluents. In this work, ozone (O 3) was investigated as a possible oxidizing agent to remove fishery antibiotics from aquaculture effluents: florfenicol (FF), oxytetracycline (OTC), sulfadimethoxine (SDM), sulfamethoxazole (SMX), and trimethoprim (TMP). Batch experiments were performed using ultrapure water and aquaculture effluents spiked with a mixture of target antibiotics at relatively high concentrations (10 mg L-1 each). OTC, SMX and TMP were fully removed (< 30 min) regardless of the tested conditions, mainly by O 3 direct attack. In contrast, FF was partially removed in 30 min (∼ 10 and 60%, in aquaculture effluents and ultrapure water, respectively), but only in the presence of hydroxyl radicals (HO•), the FF concentrations reaching levels below the detection limits in ultrapure water after 60 min. In the case of SDM, its degradation was highly influenced by the selected water matrix, but with removals always higher than 68%. In continuous-flow experiments applying more environmentally relevant antibiotic concentrations (100 ng L-1 each) and low O 3 doses (1.5 mg L−1), ozonation highly removed (> 98%) all tested antibiotics from aquaculture effluents with a hydraulic retention time (HRT) of 10 min, except FF (68%). Although by-products were detected in treated samples, zebrafish (Danio rerio) embryotoxicity tests did not show a toxicity increase by applying this ozonation treatment. Ozonation is thus a possible solution to remove antibiotics from aquaculture effluents. Still, full-scale studies in aquaculture farms are needed, and generation of HO• may be favoured to readily oxidize the FF antibiotic. [Display omitted] [ABSTRACT FROM AUTHOR]

This review aims to present the issues associated to enantioseparation of chiral pharmaceuticals in biological and environmental matrices using chiral stationary phases (CSP). Thus, it related some enantioselective methods in liquid chromatography (LC) and compares the importance given to chiral separation in biomedical and environmental fields. For that the most used CSP, the enantioselective chromatographic methods, their advantages and drawbacks were swiftly revised and compared. The recent advances and the limitations of chiral analytical methods in LC were also discussed. [ABSTRACT FROM AUTHOR]

Fluoxetine (FLX) is a chiral fluorinated pharmaceutical indicated mainly for the treatment of depression and is one of the most dispensed drugs in the world. There is clear evidence of environmental contamination with this drug and its active metabolite norfluoxetine (NFLX). In this study the enantioselective biodegradation of racemic FLX and of its enantiomers by Labrys portucalensis strain F11 was assessed. When 2 μM of racemic FLX was supplemented as sole carbon source, complete removal of both enantiomers, with stoichiometric liberation of fluoride, was achieved in 30 d. For racemic FLX concentration of 4 and 9 μM, partial degradation of the enantiomers was obtained. In the presence of acetate as an additional carbon source, at 4, 9 and 21 μM of racemic FLX and at 25 μM of racemic FLX, (S)-FLX or (R)-FLX, complete degradation of the two enantiomers occurred. At higher concentrations of 45 and 89 μM of racemic FLX, partial degradation was achieved. Preferential degradation of the (R)-enantiomer was observed in all experiments. To our knowledge, this is the first time that enantioselective biodegradation of FLX by a single bacterium is reported. [ABSTRACT FROM AUTHOR]

Aquaculture is the fastest growing animal food-producing sector. Water is the central resource for aquaculture, and it is essential that its quality be preserved. Micropollutants (MPs) can reach aquaculture through anthropogenic addition or inlet water, and may cause harmful effects such as endocrine disruption and antibiotic resistance, adversely affecting the fish species being farmed. Furthermore, the discharge of aquaculture effluents into the environment may contribute to the deterioration of water courses. In this sense, the implementation of environmentally responsible measures in aquaculture farms is imperative for the protection of ecosystems and human health. The European Commission (EC) has recently launched a guiding document promoting ecological aquaculture practices; however, options for water treatment are still lacking. Conventional processes are not designed to deal with MPs; this review article consolidates relevant information on the application of advanced oxidation technologies (AOTs) and constructed wetlands (CWs) as potential strategies in this regard. Although 161 studies on the application of AOTs or CWs in aquaculture have already been published, only 34 focused on MPs (28 on AOTs and 6 on CWs), whereas the others reported the removal of contaminants such as bacteria, organic matter, solids and inorganic ions. No study coupling both treatments has been reported to date for the removal of MPs from aquaculture waters. AOTs and CWs are prospective alternatives for the treatment of aquacultural aqueous matrices. However, the type of aquaculture activity and the specifications of these available technologies should be considered while selecting the most suitable treatment option. [Display omitted] • Micropollutants in aquaculture water is a concern of the European Commission. • Chemical and biological treatments to remove these micropollutants are reviewed. • Studies with real matrices are scarce for advanced oxidation technologies (AOTs). • More studies conducted at full scale are needed for constructed wetlands (CWs). • Both AOTs and CWs can remove conventional pollutants from aquaculture waters. [ABSTRACT FROM AUTHOR]

Highlights: [•] The multi-techniques analytical approach allowed the evaluation of the degradation of fluoroquinolones by a microbial consortium. [•] Fluoride ions released exposed the incomplete mineralization of the fluoroquinolones. [•] Metabolites were identified by LC–MS/MS and QqTOF MS. [•] New structures of the intermediates were proposed. [Copyright &y& Elsevier]

Highlights: [•] Enantioseparation of fluoxetine and norfluoxetine on a Chirobiotic V. [•] Enantioselective HPLC-FD method for quantification of fluoxetine and norfluoxetine. [•] FLX was degraded in wastewater effluent samples. [ABSTRACT FROM AUTHOR]

Thymic epithelial cells (TECs) help orchestrate thymopoiesis, and TEC differentiation relies on bidirectional interactions with thymocytes. Although the molecular mediators that stimulate medullary thymic epithelial cell (mTEC) maturation are partially elucidated, the signals that regulate cortical thymic epithelial cell (cTEC) homeostasis remain elusive. Using IL-7 reporter mice, we show that TECs coexpressing high levels of IL-7 (Il7YFP+ TECs) reside within a subset of CD205+Ly51+CD40low cTECs that coexpresses Dll4, Ccl25, Ccrl1, Ctsl, Psmb11, and Prss16 and segregates from CD80+CD40high mTECs expressing Tnfrsf11a, Ctss, and Aire. As the frequency of Il7YFP+ TECs gradually declines as mTEC development unfolds, we explored the relationship between Il7YFP+ TECs and mTECs. In thymic organotypic cultures, the thymocyte-induced reduction in Il7YFP+ TECs dissociates from the receptor activator of NF-κB–mediated differentiation of CD80+ mTECs. Still, Il7YFP+ TECs can generate some CD80+ mTECs in a stepwise differentiation process via YFP−Ly51lowCD80low intermediates. Il7YFP+ TECs are sustained in Rag2−/− mice, even following in vivo anti-CD3ε treatment that mimics the process of pre-TCR β-selection of thymocytes to the double positive (DP) stage. Using Marilyn-Rag2−/− TCR transgenic, we find that positive selection into the CD4 lineage moderately reduces the frequency of Il7YFP+ TECs, whereas negative selection provokes a striking loss of Il7YFP+ TECs. These results imply that the strength of MHC/peptide–TCR interactions between TECs and thymocytes during selection constitutes a novel rheostat that controls the maintenance of IL-7–expressing cTECs. [ABSTRACT FROM AUTHOR]

The biodegradation of five pharmaceutical ingredients (PIs) of different therapeutic classes, namely antibiotics (trimethoprim, sulfametoxazole and ciprofloxacin), anti-inflammatory (diclofenac) and anti-epileptic (carbamazepine), by two distinct microbial consortia, was investigated. For the monitoring of biodegradation assays, a simple HPLC-DAD (High Performance Liquid Chromatography – Diode Array Detector) method was developed and validated. The separation of the target pharmaceuticals was performed using an environmental friendly mobile phase in a gradient mode of 0.1% triethylamine (TEA) in water acidified at pH 2.23 with trifluoroacetic acid (TFAA) and ethanol as organic solvent. The method revealed to be selective, linear and precise in the range of 1.0 to 30.0 μg/mL for all PIs. Biodegradation assays were performed using activated sludge and a bacterial consortium (able to degrade fluoroaromatic compounds) supplemented with the target PIs at a final concentration of 25 μg/mL. The results revealed that activated sludge removed the target compounds more efficiently than the bacterial consortium. [ABSTRACT FROM AUTHOR]

Mutable collagenous tissues (MCTs) of echinoderms show reversible changes in tensile properties (mutability) that are initiated and modulated by the nervous system via the activities of cells known as juxtaligamental cells. The molecular mechanism underpinning this mechanical adaptability has still to be elucidated. Adaptable connective tissues are also present in mammals, most notably in the uterine cervix, in which changes in stiffness result partly from changes in the balance between matrix metalloproteinases (MMPs) and tissue inhibitors of metalloproteinases (TIMPs). There have been no attempts to assess the potential involvement of MMPs in the echinoderm mutability phenomenon, apart from studies dealing with a process whose relationship to the latter is uncertain. In this investigation we used the compass depressor ligaments (CDLs) of the sea-urchin Paracentrotus lividus. The effect of a synthetic MMP inhibitor - galardin - on the biomechanical properties of CDLs in different mechanical states (''standard'', ''compliant'' and ''stiff'') was evaluated by dynamic mechanical analysis, and the presence of MMPs in normal and galardin-treated CDLs was determined semi-quantitatively by gelatin zymography. Galardin reversibly increased the stiffness and storage modulus of CDLs in all three states, although its effect was significantly lower in stiff than in standard or compliant CDLs. Gelatin zymography revealed a progressive increase in total gelatinolytic activity between the compliant, standard and stiff states, which was possibly due primarily to higher molecular weight components resulting from the inhibition and degradation of MMPs. Galardin caused no change in the gelatinolytic activity of stiff CDLs, a pronounced and statistically significant reduction in that of standard CDLs, and a pronounced, but not statistically significant, reduction in that of compliant CDLs. Our results provide evidence that MMPs may contribute to the variable tensility of the CDLs, in the light of which we provide an updated hypothesis for the regulatory mechanism controlling MCT mutability. [ABSTRACT FROM AUTHOR]

The mutable collagenous tissue (MCT) of echinoderms has the ability to undergo rapid and reversible changes in passive mechanical properties that are initiated and modulated by the nervous system. Since the mechanism of MCT mutability is poorly understood, the aim of this work was to provide a detailed morphological analysis of a typical mutable collagenous structure in its different mechanical states. The model studied was the compass depressor ligament (CDL) of a sea urchin (Paracentrotus lividus), which was characterized in different functional states mimicking MCT mutability. Transmission electron microscopy, histochemistry, cryo-scanning electron microscopy, focused ion beam/scanning electron microscopy, and field emission gun-environmental scanning electron microscopy were used to visualize CDLs at the micro- and nanoscales. This investigation has revealed previously unreported differences in both extracellular and cellular constituents, expanding the current knowledge of the relationship between the organization of the CDL and its mechanical state. Scanning electron microscopies in particular provided a three-dimensional overview of CDL architecture at the micro- and nano-scales, and clarified the micro-organization of the ECM components that are involved in mutability. Further evidence that the juxtaligamental cells are the effectors of these changes in mechanical properties was provided by a correlation between their cytology and the tensile state of the CDLs. [ABSTRACT FROM AUTHOR]

Carbon xerogels (CXs) were synthesized by polycondensation of resorcinol and formaldehyde, followed by thermal annealing, and subjected to hydrothermal oxidation. Solid-phase extraction (SPE) cartridges were filled with CXs and tested for extraction of metaflumizone and other seven environmental micropollutants (acetamiprid, atrazine, isoproturon, methiocarb, carbamazepine, diclofenac, and perfluorooctanesulfonic acid) before chromatographic analysis. The recoveries obtained with the pristine CX were low for most analytes, except for metaflumizone (69 ± 5%). Moreover, it was concluded that the adsorption/desorption process of the micropollutants performed better on CXs with a less acidic surface (i.e., pristine CX). Thus, cartridges were prepared with pristine CX and multi-walled carbon nanotubes (MWCNTs) in a multi-layer configuration. This reusable cartridge was able to simultaneously extract the eight micropollutants and was used to validate an analytical methodology based on SPE followed by ultra-high performance liquid chromatography-tandem mass spectrometry. A widespread occurrence of 6/8 target compounds was observed in surface water collected in rivers supplying three drinking water treatment plants and in the resulting drinking water at the endpoint of each distribution system. Therefore, the first study employing CXs and MWCNTs as sorbent in multi-layer SPE cartridges is herein reported as a proof of concept for determination of multi-class water micropollutants. [ABSTRACT FROM AUTHOR]

Numerous contaminants of emerging concern (CECs) have been found in different water bodies. Directive 2013/39/EU and Decision 2018/840/EU are consequently being implemented in the field of water policies. Twelve CECs (e.g., isoproturon, ciprofloxacin, and clarithromycin are among those listed) were detected in a municipal wastewater secondary effluent by means of solid phase extraction and ultra-high-performance liquid chromatography with tandem mass spectrometry (SPE-UHPLC-MS/MS). Different advanced oxidation processes (AOPs), based on the combination of ozone, UVA-LED and powdered TiO2, were investigated for their removal in a semi-batch operation. In addition, TiO2-coated glass rings (P25R) were characterized with different techniques (SEM, WDXRF) and used for continuous mode operation in a packed bed reactor (PBR). Among the AOPs studied, ozone-based processes were found to be more efficient than heterogeneous photocatalysis. A kinetic study was performed showing that direct ozonation is the main oxidation pathway for CEC removal. Ozone was successfully decomposed in combination with UVA-LED and P25R, resulting in an apparent rate constant of 3.2 × 10−2 s−1 higher than in the O3/LED system (1.0 × 10−3 s−1) or with ozone alone (8.6 × 10−5 s−1). Hydroxyl radical reaction could prevail over direct ozone reaction for the most refractory compounds (e.g., isoproturon). [ABSTRACT FROM AUTHOR]

Pristine and functionalized multi-walled carbon nanotubes (MWCNTs) were investigated as adsorbent materials inside solid-phase extraction (SPE) cartridges for extraction and preconcentration of 8 EU-relevant organic micropollutants (with different pKa and polarity) before chromatographic analysis of surface water. The recoveries obtained were > 60% for 5/8 target pollutants (acetamiprid, atrazine, carbamazepine, diclofenac, and isoproturon) using a low amount of this reusable adsorbent (50 mg) and an eco-friendly solvent (ethanol) for both conditioning and elution steps. The introduction of oxygenated surface groups in the carbon nanotubes by using a controlled HNO3 hydrothermal oxidation method, considerably improved the recoveries obtained for PFOS (perfluorooctanesulfonic acid) and methiocarb, which was ascribed to the hydrogen bond adsorption mechanism, but decreased those observed for the pesticide acetamiprid and for two pharmaceuticals (carbamazepine and diclofenac), suggesting π–π dispersive interactions. Moreover, a good correlation was found between the recovery obtained for methiocarb and the amount of oxygenated surface groups on functionalized MWCNTs, which was mainly attributed to the increase of phenols and carbonyl and quinone groups. Thus, the HNO3 hydrothermal oxidation method can be used to finely tune the surface chemistry (and texture) of MWCNTs according to the specific micropollutants to be extracted and quantified in real water samples. [ABSTRACT FROM AUTHOR]

• Municipal wastewater (MWW) was treated by advanced oxidation technologies (AOTs). • Direct contact membrane distillation (DCMD) was investigated as post-treatment. • Ozonation was efficient to remove 12 micropollutants (MPs) determined in MWW. • UV/H 2 O 2 as pre-treatment minimized the flux decline. • Flux decline was strongly related to the DOC content of the DCMD feed. In this work, the combination of advanced oxidation technologies (AOTs) and direct contact membrane distillation (DCMD) was investigated for the treatment of municipal wastewater collected from the secondary clarifier of a municipal wastewater treatment plant (MWWTP). Average removal efficiencies of the 12 micropollutants present in the wastewater samples were higher than 95 % with ozonation (O 3) and photolytic ozonation (UV/O 3), whereas only near 50 % of removal efficiency was achieved with UV-peroxidation (UV/H 2 O 2). When the ozone-based processes were combined with DCMD, the concentration of these micropollutants were below the detection limits in the respective permeate, increasing the quality of the treated water. However, the permeate fluxes in DCMD were remarkably higher when the wastewater was pre-treated with UV/H 2 O 2 instead of O 3 , most probably due to the better disinfection achieved by UV/H 2 O 2. It was also confirmed that the dissolved organic carbon (DOC) of the wastewater strongly affects the permeate fluxes achieved by DCMD. In this regard, the combination of the oxidation and membrane separation processes is more appropriate for wastewaters with low DOC contents (< 15 mg L−1). [ABSTRACT FROM AUTHOR]

Graphical abstract Highlights • Exfoliated graphitic carbon nitride (g-C 3 N 4) was synthesised and characterized. • The metal-free photocatalyst was studied under visible light. • Efficient removal of micropollutants from secondary urban wastewater was achieved. • g-C 3 N 4 was supported on glass rings to avoid its recovery from treated wastewater. Abstract Heterogeneous photocatalysis under visible light was employed for the degradation of organic micropollutants (MPs) found in the biologically treated effluents of an urban wastewater treatment plant (UWWTP). The irradiation source consisted in 4 light emitting diodes (LEDs) with a nominal power of 400–500 W m–2 at 417 nm. Metal-free exfoliated graphitic carbon nitride (gCN T), which was synthetized through a simple thermal treatment using dicyandiamide as precursor, was employed as photocatalyst. The gCN T material was characterized using different techniques: N 2 adsorption isotherms at 77 K, electron microscopy (scanning and transmission) and diffuse reflectance UV–Vis. The photocatalytic performance of the material was compared to the commercial TiO 2 -P25, confirming that gCN T led to a remarkable higher removal efficiency of the target MPs. Most of these MPs were removed in less than 10 min to levels below the limit of quantification (carbamazepine > isoproturon > clopidogrel > diclofenac > atenolol > bezafibrate > tramadol > venlafaxine > fluoxetine). Indirect photolysis, resulting from the secondary reactive oxidants generated during the irradiation of the aqueous matrix components, was found to partially contribute for the elimination of the occurring MPs. In addition, the gCN T photocatalyst was immobilized on glass rings for use under continuous mode operation, a minimum residence time of 25 min being required to attain significant removal efficiencies. Phytotoxicity experiments showed that heterogeneous photocatalysis did not enhance the toxicity of the wastewaters. [ABSTRACT FROM AUTHOR]

Graphical abstract Highlights • Antibiotics, bacteria and ARB removal in secondary treated urban wastewater. • Antibiotics are efficiently oxidized by TiO 2 -photocatalysis with UVA-LEDs. • Methanol has a scavenging effect on the removal of the antibiotics. • Efficient inactivation of cultivable bacteria including those antibiotic resistant. • Bacterial regrowth is observed after 3-days storage of treated wastewater. Abstract Secondary urban wastewater samples were spiked with azithromycin (AZT), trimethoprim (TMP), ofloxacin (OFL) and sulfamethoxazole (SMX) at 100 µg L−1 to investigate the efficiency of a TiO 2 -photocatalytic treatment using UVA-LEDs. Different operating parameters were studied, such as the irradiation conditions, catalyst load and the use of methanol as carrier solvent and radical scavenger. The most efficient conditions to treat spiked urban wastewater (4 LEDs symmetrically distributed and 1.00 g L−1 of catalyst) were also assessed on the removal of the antibiotics at real concentrations, as well as on the inactivation and regrowth of bacteria after 3-day storage (total and resistant heterotrophs, Escherichia coli and enterococci). Clindamycin (CLI) was targeted when SMX was not detected. One-hour treatment was enough to reduce the analysed antibiotics to values below the detection limits and to decrease the bacterial load by 2 log-units. Bacterial regrowth was observed for total heterotrophs, after the storage of photocatalytic treated wastewater, to values close to pre-treatment. However, the antibiotic resistance percentage of such stored wastewater was always similar or lower than that of secondary urban wastewater. Thus, the potential of this process as part of the tertiary treatment is demonstrated, but conditions must be adjusted to minimize microbial regrowth. [ABSTRACT FROM AUTHOR]

Degradation and mineralization of ibuprofen (IBU) were investigated using Ultraviolet (UV) Light Emitting Diodes (LEDs) in TiO 2 photocatalysis. Samples of ultrapure water (UP) and a secondary treated effluent of a municipal wastewater treatment plant (WWTP), both spiked with IBU, as well as a highly concentrated IBU (230 mg L −1 ) pharmaceutical industry wastewater (PIWW), were tested in the TiO 2 /UV-LED system. Three operating parameters, namely, pH, catalyst load and number of LEDs were optimized. The process efficiency was evaluated in terms of IBU removal using high performance liquid chromatography (HPLC) and ultra-high performance liquid chromatography coupled to tandem mass spectrometry (UHPLC-MS/MS). Additionally, the mineralization was investigated by determining the dissolved organic carbon (DOC) content. The chemical structures of transformation products were proposed based on the data obtained using liquid chromatography with a high resolution mass spectrometer ion trap/time-of-flight (LC-MS-IT-TOF). A possible pathway of IBU degradation was accordingly suggested. Bioassays were performed using the marine bacterium Vibrio fischeri to evaluate the potential acute toxicity of original and treated wastewaters. TiO 2 heterogeneous photocatalysis was efficient to remove IBU from UP and from PIWW, and less efficient in treating the wastewater from the municipal WWTP. The acute toxicity decreased by ca. 40% after treatment, regardless of the studied matrix. [ABSTRACT FROM AUTHOR]

The decoration of titanium (Ti) implant surfaces with TiO 2 nanotubes has emerged as a promising strategy to improve osseointegration and avoid infection. Nevertheless, it has been reported that nanotubular films are prone to peeling off from the Ti substrate due to the poor interfacial adhesion. The knowledge on the interfacial properties of such interface, although not well explored, is crucial for understanding the mechanisms behind the poor adhesion problem of these films and to further achieve an easy and effective solution to solve it. This paper is focused on the bio-functionalization of TiO 2 nanotubular films with zinc (Zn) as an antimicrobial and bone healing agent, together with two major components of bone matrix, namely calcium (Ca) and phosphorous (P). The main aim is, for the first time, the thorough characterization of the interface between TiO 2 nanotubes and the Ti substrate, along with the better understanding of the bio-functionalization mechanisms of TiO 2 nanotubes and their influence on the interfacial features of the films. TiO 2 nanotubes were successfully synthesized by two-step anodization and their bio-functionalization with Ca, P and Zn was achieved by reverse polarization anodization treatments. The in-depth characterization of the morphological and chemical features of TiO 2 nanotubes was carried out along their length by scanning transmission electron microscopy (STEM) and energy dispersive X-ray spectroscopy (EDS), before and after bio-functionalization treatments. STEM images showed that the interface between conventional TiO 2 nanotubes and Ti is non-continuous due to the existence of a hollow space. However, bio-functionalized TiO 2 nanotubes evidenced an interface with different features, due to the formation of an interfacial oxide film as a consequence of anodization, with a thickness comprised between 230 and 250 nm. The results presented in this work may inspire the emergence of novel surface treatment strategies seeking the long-term performance of metallic-modified osseointegrated implants. [ABSTRACT FROM AUTHOR]

It has been shown that the synthesis of TiO 2 nanotubes by anodization provides outstanding properties to Ti surfaces intended for dental and orthopedic implants applications. Beyond the very well-known potential of these surfaces to improve osseointegration and avoid infection, the knowledge on the adhesion and degradation behavior of TiO 2 nanotubes under the simultaneous action of wear and corrosion is still poorly understood and these are issues of tremendous importance. The main aim of this work is to investigate, for the first time, the tribo-electrochemical degradation behavior of Ti surfaces decorated with TiO 2 nanotubes before and after bio-functionalization treatments. Well-aligned TiO 2 nanotubes (NTs) were produced containing elements natively present in bone such as calcium (Ca) and phosphorous (P), in addition of zinc (Zn) as an antimicrobial agent and stimulator of bone formation. The synthesis of Ca/P/Zn-doped nanotubes (NT-Ca/P/Zn) was achieved by reverse polarization and anodization treatments applied to conventional TiO 2 nanotubes grown by two-step anodization. The nanotube surfaces were analyzed by scanning electron microscopy (SEM) while dark-field scanning transmission electron microscopy (STEM-DF) was used to characterize the Ti/TiO 2 nanotubular films interfaces. Tribo-electrochemical tests were conducted under reciprocating sliding conditions in artificial saliva. The open circuit potential (OCP) was monitored before, during and after sliding tests, and the coefficient of friction (COF) values were registered during rubbing action. The wear tracks resulting from sliding tests were characterized by SEM and wear volume measurements were carried out by 2D profilometry. The results show that the tribo-electrochemical behavior of TiO 2 nanotubes was significantly improved after bio-functionalization treatments. The higher electrochemical stability and lower mechanical degradation of these films was correlated with their improved adhesion strength to Ti substrate, which is granted by the nano-thick oxide film formed at the interface region, during bio-functionalization processes. A first insight on the degradation mechanisms taking place during tribo-electrochemical action is proposed. The outcomes of this study may contribute in a great extent for the development of new implant surfaces with improved biomechanical stability and thus contribute for the long term success of dental implants. [ABSTRACT FROM AUTHOR]

Eighteen per-and polyfluoroalkyl substances (PFASs) were investigated in surface waters of four river basins in Portugal (Ave, Leça, Antuã, and Cértima) during the dry and wet seasons. All sampling sites showed contamination in at least one of the seasons. In the dry season, perfluorooctanoate acid (PFOA) and perfluoro-octane sulfonate (PFOS), were the most frequent PFASs, while during the wet season these were PFOA and perfluobutane-sulfonic acid (PFBS). Compounds detected at higher concentrations were PFOS (22.6 ng L−1) and perfluoro-butanoic acid (PFBA) (22.6 ng L−1) in the dry and wet seasons, respectively. Moreover, the prospective environmental risks of PFASs, detected at higher concentrations, were evaluated based on the Risk Quotient (RQ) classification, which comprises acute and chronic toxicity. The results show that the RQ values of eight out of the nine PFASs were below 0.01, indicating low risk to organisms at different trophic levels in the four rivers in both seasons, wet and dry. Nevertheless, in the specific case of perfluoro-tetradecanoic acid (PFTeA), the RQ values calculated exceeded 1 for fish (96 h) and daphnids (48 h), indicating a high risk for these organisms. Furthermore, the RQ values were higher than 0.1, indicating a medium risk for fish, daphnids and green algae (96 h). [ABSTRACT FROM AUTHOR]

An aerobic granular sludge-sequencing batch reactor (AGS-SBR) was fed for 28-days with a simulated wastewater containing a mixture of chiral pharmaceuticals (CPs) (alprenolol, bisoprolol, metoprolol, propranolol, venlafaxine, salbutamol, fluoxetine and norfluoxetine), each at 1.3 μg L −1 . AGS-SBR exhibited the highest removal efficiency for norfluoxetine, with preferential removal of the ( R )-enantiomer indicating that biological-mediated processes occurred. For all other CPs, removal was non-enantioselective, occurring through biosorption onto AGS. A gradual decline of CPs removal was observed, probably related to the decrease of AGS adsorption capacity. Moreover, chemical oxygen demand (COD) content in the bulk liquid after anaerobic feeding increased, and P-release dropped, probably because the polyphosphate-accumulating organism's activity was affected. Nitrification was also affected as indicated by the ammonium effluent concentration increase. Moreover, CPs exposure promoted AGS disintegration, with decreasing granule size. After stopping CPs feeding, the AGS started to recover its compact structure, and the system returned its normal performance concerning COD- and P-removal. N-removal seemed to be a more sensitive process, as while the ammonium levels were fully restored at the end of operation, nitrite reduction was only partially restored. Results provide useful information on AGS performance during the treatment of wastewater containing pharmaceuticals, a frequent scenario in WWTP. [ABSTRACT FROM AUTHOR]

Natural organic compounds such as phytoestrogens and phytosterols found in various plants, as well as mycotoxins produced by fungi, can be found in aquatic environments. The aim of this study was to investigate the occurrence of three different classes of natural estrogenic compounds, i.e., phytoestrogens, phytosterols and mycotoxins, in estuarine water samples from the Ave River estuary. For that, water samples were collected at five sampling points distributed along the estuary at low tide, during 1 year, processed by solid-phase extraction (SPE) and analyzed by gas chromatography coupled to mass spectrometry (GC–MS). To correlate the presence of phytoestrogens and phytosterols in the estuarine water, local flora was collected on riverside. Trace elements content and physicochemical parameters such as nutrients and dissolved oxygen were also determined seasonally at each sampling point, to give insights for the evaluation of water quality and anthropogenic pressure. Both phytoestrogens and phytosterols showed a seasonal variation, with the highest values observed in spring and summer and the lowest in winter. Daidzein (DAID) was found up to 404.0 ng L−1in spring and coumestrol (COUM) was found up to 165.0 ng L−1in summer. The mycotoxin deoxynivalenol (DON) was ubiquitously determined with values ranging from 59.5 to 642.4 ng L−1. Nutrients and metals distribution and concentration varied among sampling stations and seasons. This study revealed for the first time the presence of mycotoxins, various classes of phytoestrogens and stigmasterol (STG) in estuarine water from the Ave River (Portugal), and the evaluation of the water quality confirmed that this estuary is still highly impacted by anthropogenic activities. [ABSTRACT FROM PUBLISHER]

Although there are no legal discharge limits for micropollutants into the environment, some regulations have been published in the last few years. Recently, a watch list of substances for European Union-wide monitoring was reported in the Decision 2015/495/EU of 20 March 2015. Besides the substances previously recommended to be included by the Directive 39/2013/EU, namely two pharmaceuticals (diclofenac and the synthetic hormone 17-alpha-ethinylestradiol (EE2)) and a natural hormone (17-beta-estradiol (E2)), the first watch list of 10 substances/groups of substances also refers three macrolide antibiotics (azithromycin, clarithromycin and erythromycin), other natural hormone (estrone (E1)), some pesticides (methiocarb, oxadiazon, imidacloprid, thiacloprid, thiamethoxam, clothianidin, acetamiprid and triallate), a UV filter (2-ethylhexyl-4-methoxycinnamate) and an antioxidant (2,6-di-tert-butyl-4-methylphenol) commonly used as food additive. Since little is known about the removal of most of the substances included in the Decision 2015/495/EU, particularly regarding realistic concentrations in aqueous environmental samples, this review aims to: (i) overview the European policy in the water field; (ii) briefly describe the most commonly used conventional and advanced treatment processes to remove micropollutants; (iii) summarize the relevant data published in the last decade, regarding occurrence and removal in aqueous matrices of the 10 substances/groups of substances that were recently included in the first watch list for European Union monitoring (Decision 2015/495/EU); and (iv) highlight the lack of reports concerning some substances of the watch list, the study of un-spiked aquatic matrices and the assessment of transformation by-products. [ABSTRACT FROM AUTHOR]

The degradation of two organic pollutants (amoxicillin and diclofenac) in 0.1 mM aqueous solutions was studied by using advanced oxidation processes, namely ozonation, photolysis, photolytic ozonation, photocatalysis and photocatalytic ozonation. Diclofenac was degraded quickly under direct photolysis by artificial light (medium-pressure vapor arc, λ exc > 300 nm), while amoxicillin remained very stable. In the presence of ozone, regardless of the type of process, complete degradation of both organic pollutants was observed in less than 20 min. Photolysis or ozonation on their own led to modest values of total organic carbon (TOC) removal (<6% or 41%, respectively in 180 min), while for photocatalysis (no ozone present) a significant fraction of nonoxidizable compounds remained in the treated water (∼15% after 180 min). In the case of photolytic ozonation, the kinetics of TOC removal was slow. In contrast, a relatively fast and complete mineralization of amoxicillin and diclofenac (30 and 120 min, respectively) was achieved when applying the photocatalytic ozonation process. The absence of toxicity of the treated waters was confirmed by growth inhibition assays using two different microorganisms, Escherichia coli and Staphylococcus aureus . Photocatalytic ozonation was also applied to an urban wastewater spiked with both amoxicillin and diclofenac. The parent pollutants were easily oxidized, but the TOC removal was only as much as 68%, mainly due to the persistent presence of oxamic acid in the treated sample. The same treatment allowed the effective degradation of a wide group of micropollutants (pesticides, pharmaceuticals, hormones and an industrial compound) detected in non-spiked urban wastewater. [ABSTRACT FROM AUTHOR]

The use of nanomaterials has been increasing in recent times, and they are widely used in industries such as cosmetics, drugs, food, water treatment, and agriculture. The rapid development of new nanomaterials demands a set of approaches to evaluate the potential toxicity and risks related to them. In this regard, nanosafety has been using and adapting already existing methods (toxicological approach), but the unique characteristics of nanomaterials demand new approaches (nanotoxicology) to fully understand the potential toxicity, immunotoxicity, and (epi)genotoxicity. In addition, new technologies, such as organs-on-chips and sophisticated sensors, are under development and/or adaptation. All the information generated is used to develop new in silico approaches trying to predict the potential effects of newly developed materials. The overall evaluation of nanomaterials from their production to their final disposal chain is completed using the life cycle assessment (LCA), which is becoming an important element of nanosafety considering sustainability and environmental impact. In this review, we give an overview of all these elements of nanosafety. [ABSTRACT FROM AUTHOR]

The viscoelastic properties of vertebrate connective tissues rarely undergo significant changes within physiological timescales, the only major exception being the reversible destiffening of the mammalian uterine cervix at the end of pregnancy. In contrast to this, the connective tissues of echinoderms (sea urchins, starfish, sea cucumbers, etc.) can switch reversibly between stiff and compliant conditions in timescales of around a second to minutes. Elucidation of the molecular mechanism underlying such mutability has implications for the zoological, ecological and evolutionary field. Important information could also arise for veterinary and biomedical sciences, particularly regarding the pathological plasticization or stiffening of connective tissue structures. In the present investigation we analyzed aspects of the ultrastructure and biochemistry in two representative models, the compass depressor ligament and the peristomial membrane of the edible sea urchin Paracentrotus lividus , compared in three different mechanical states. The results provide further evidence that the mechanical adaptability of echinoderm connective tissues does not necessarily imply changes in the collagen fibrils themselves. The higher glycosaminoglycan (GAG) content registered in the peristomial membrane with respect to the compass depressor ligament suggests a diverse role of these molecules in the two mutable collagenous tissues. The possible involvement of GAG in the mutability phenomenon will need further clarification. During the shift from a compliant to a standard condition, significant changes in GAG content were detected only in the compass depressor ligament. Similarities in terms of ultrastructure (collagen fibrillar assembling) and biochemistry (two alpha chains) were found between the two models and mammalian collagen. Nevertheless, differences in collagen immunoreactivity, alpha chain migration on SDS-PAGE and BLAST alignment highlighted the uniqueness of sea urchin collagen with respect to mammalian collagen. [ABSTRACT FROM AUTHOR]

Fluoxetine (FLX) is a chiral fluorinated pharmaceutical mainly indicated for treatment of depression and is one of the most distributed drugs. There is a clear evidence of environmental contamination with this drug. Aerobic granular sludge sequencing batch reactors constitute a promising technology for wastewater treatment; however the removal of carbon and nutrients can be affected by micropollutants. In this study, the fate and effect of FLX on reactor performance and on microbial population were investigated. FLX adsorption/desorption to the aerobic granules was observed. FLX shock loads (≤4 μM) did not show a significant effect on the COD removal. Ammonium removal efficiency decreased in the beginning of first shock load, but after 20 days, ammonia oxidizing bacteria became adapted. The nitrite concentration in the effluent was practically null indicating that nitrite oxidizing bacteria was not inhibited, whereas, nitrate was accumulated in the effluent, indicating that denitrification was affected. Phosphate removal was affected at the beginning showing a gradual adaptation, and the effluent concentration was <0.04 mM after 70 days. A shift in microbial community occurred probably due to FLX exposure, which induced adaptation/restructuration of the microbial population. This contributed to the robustness of the reactor, which was able to adapt to the FLX load. [ABSTRACT FROM AUTHOR]

The progressively increasing use of nanomaterials (NMs) has awakened issues related to nanosafety and its potential toxic effects on human health. Emerging studies suggest that NMs alter cell communication by reshaping and altering the secretion of extracellular vesicles (EVs), leading to dysfunction in recipient cells. However, there is limited understanding of how the physicochemical characteristics of NMs alter the EV content and their consequent physiological functions. Therefore, this review explored the relevance of EVs in the nanotoxicology field. The current state of the art on how EVs are modulated by NM exposure and the possible regulation and modulation of signaling pathways and physiological responses were assessed in detail. This review followed the manual for reviewers produced by The Joanna Brigs Institute for Scoping Reviews and the PRISMA extension for Scoping Reviews (PRISMA-ScR): checklist and explanation. The research question, "Do NMs modulate cellular responses mediated by EVs?" was analyzed following the PECO model (P (Population) = EVs, E (Exposure) = NMs, C (Comparator) = EVs without exposure to NMs, O (Outcome) = Cellular responses/change in EVs) to help methodologically assess the association between exposure and outcome. For each theme in the PECO acronym, keywords were defined, organized, and researched in PubMed, Science Direct, Scopus, Web of Science, EMBASE, and Cochrane databases, up to 30 September 2021. In vitro, in vivo, ex vivo, and clinical studies that analyzed the effect of NMs on EV biogenesis, cargo, and cellular responses were included in the analysis. The methodological quality assessment was conducted using the ToxRTool, ARRIVE guideline, Newcastle Ottawa and the EV-TRACK platform. The search in the referred databases identified 2944 articles. After applying the eligibility criteria and two-step screening, 18 articles were included in the final review. We observed that depending on the concentration and physicochemical characteristics, specific NMs promote a significant increase in EV secretion as well as changes in their cargo, especially regarding the expression of proteins and miRNAs, which, in turn, were involved in biological processes that included cell communication, angiogenesis, and activation of the immune response, etc. Although further studies are necessary, this work suggests that molecular investigations on EVs induced by NM exposure may become a potential tool for toxicological studies since they are widely accessible biomarkers that may form a bridge between NM exposure and the cellular response and pathological outcome. [ABSTRACT FROM AUTHOR]

[Display omitted] • TiO 2 was grown and crystallized on polysulfone, PTFE and PVDF membranes. • Diclofenac and 17α-ethinylestradiol were removed by adsorption and photocatalysis. • 17α-ethinylestradiol was preferentially adsorbed regardless of the membrane tested. • TiO 2 -polysulfone was the most active membrane for the removal of both pollutants. • TiO 2 -PVDF presented the highest stability in consecutive reaction cycles. TiO 2 in situ growth on three commercial membranes (polysulfone – PS, polyvinylidene fluoride – PVDF and polytetrafluoroethylene – PTFE) and its hydrothermal post-crystallization to transform TiO 2 into a photocatalytically-active phase, were investigated under mild synthesis conditions to preserve the textural properties of the supports. The membranes were successfully prepared and characterized by scanning electron microscopy, thermogravimetry analysis, N 2 physisorption, X-ray diffraction, and water contact angle measurements, among other techniques. Membrane supports with a more opened porosity and high hydrophilicity allowed to enhance the content and distribution of the anatase TiO 2 nanoparticles on the membrane surface. The efficiency and the permeate flux of the developed membranes were investigated to simultaneously remove diclofenac (DCF) and 17α-ethinylestradiol (EE2) from water by adsorption and UV–LED (light-emitting diode) photocatalysis under continuous recirculating mode. All TiO 2 membranes achieved removal efficiencies above 90% for both contaminants, EE2 being always preferentially adsorbed over DCF due to electrostatic repulsions between the DCF molecules and the surface of these membranes. The permeate flux of TiO 2 membranes was enhanced after UV-LED exposure as a consequence of the degradation of the contaminants adsorbed on the membrane surface during the dark phase. Moreover, the stability of TiO 2 nanoparticles on these membranes was studied by static tests under sonication and several consecutive reaction cycles. The TiO 2 membrane prepared with PVDF was the most stable, also presenting a high photocatalytic activity. [ABSTRACT FROM AUTHOR]

[Display omitted] • DEP exposure impairs C. elegans behaviour: Reduced speed and swimming activity. • DEP-treated worms manifest ∼50 % degeneration in glutamatergic neurons. • After exposure, ∼16 % of CEP dopaminergic neurons exhibit structural deformities. • In silico docking unveil DEP's strong binding affinity to glutamatergic transporter. • DEP induces developmental delays and antioxidant enzyme (sod-3 & gst-4) expression. The growing body of evidence links exposure to particulate matter pollutants with an increased risk of neurodegenerative diseases. In the present study, we investigated whether diesel exhaust particles can induce neurobehavioral alterations associated with neurodegenerative effects on glutamatergic and dopaminergic neurons in Caenorhabditis elegans (C. elegans). Exposure to DEP at concentrations of 0.167 µg/cm2 and 1.67 µg/cm2 resulted in significant developmental delays and altered locomotion behaviour. These effects were accompanied by discernible alterations in the expressions of antioxidant genes sod-3 and gst-4 observed in transgenic strains. Behaviour analysis demonstrated a significant reduction in average speed (p < 0.001), altered paths, and decreased swimming activities (p < 0.01), particularly at mid and high doses. Subsequent assessment of neurodegeneration markers in glutamatergic (DA1240) and dopaminergic (BZ555) transgenic worms revealed notable glutamatergic neuron degeneration at 0.167 μg/cm2 (∼30 % moderate, ∼20 % advanced) and 1.67 μg/cm2 (∼28 % moderate, ∼24 % advanced, p < 0.0001), while dopaminergic neurons exhibited structural deformities (∼16 %) without significant degeneration in terms of blebs and breaks. Furthermore, in silico docking simulations suggest the presence of an antagonistic competitive inhibition induced by DEP in the evaluated neuro-targets, stronger for the glutamatergic transporter than for the dopaminergic receptor from the comparative binding affinity point of view. The results underscore DEP's distinctive neurodegenerative effects and suggest a link between locomotion defects and glutamatergic neurodegeneration in C. elegans , providing insights into environmental health risks assessment. [ABSTRACT FROM AUTHOR]

This is the report clarifying the orientation dependence of the wear behavior of Co–Cr–Mo alloy. The wear resistance of the Co–Cr–Mo alloy with face-centered cubic (fcc) structure was found to be higher on the planes in order of {110}, {001} and {111}. Quantitatively, the wear resistance on {110} is 1.5 times larger than that on {111}. The tendency showed in coincident with the orientation dependence of the surface hardness, as empirically suggested. However, we additionally found in the observation of the worn surface in the fcc-single crystals that the volume fraction of the hexagonal close-packed (hcp)-phase, which was formed as the strain-induced martensite during the wear test, was larger in the same order of the wear resistance. The variation in formation frequency of the hcp-phase during the wear test can be explained by focusing on the Schmid factor along the resultant direction of the applied stress and the friction stress. On the {111} surface where the Schmid factor for the strain-induced ε-martensite formation is small, homogeneous deformation microstructure covered by it was not developed even after long-time wear, resulting in lower wear resistance. The results strongly suggest that not only the hardness, but the distribution of the ε-martensite is important to control the wear behavior of the Co–Cr alloys with the extremely low stacking fault energy, and it can be achieved by the crystal orientation control in the γ-phase. [Display omitted] • Orientation dependence of the wear behavior of Co–Cr–Mo alloy was first clarified. • Quantitatively, the wear resistance on {110} is 1.5 times larger than that on {111}. • Strain-induced hcp-phase martensite formation behavior strongly affects the wear resistance. • Design of novel "single-crystalline implant" with much superior properties is expected. [ABSTRACT FROM AUTHOR]

• ACE synergy with CHT and ALG improved the system physical and biological features; • Swelling influences mainly the diameter of the samples reaching an increase of 134 %. • The films sustainably release ACE to the media acting as a drug delivery device. • ACE release into the site may reinforce the biological benefits of the systems. • ACE-based films have a non-cytotoxic profile and a positive biological performance The exploitation of natural origin macromolecules, as complex physical mixtures or drugs, increases in biomedical or tissue engineering (TE) solutions. Aloe Vera is a highly explored medicinal plant, from which the main polysaccharide is acemannan (ACE). The ACE combination with chitosan and alginate results in interactions that lead to mixed junction zones formation, predicting membrane functionality improvement. This work proposes the development and characterization of ACE-based blended films as a promising strategy to design a nature-derived bioactive platform. The results confirmed that stable complex polyelectrolyte structures were formed through different intermolecular interactions. The films present good dimensional stability, flexibility, an adequate swelling ability with mostly radial water uptake, and a sustainable ACE release to the medium. Positive biological performance of the ACE-based blended films with L929 cells also suggested that they can be applied in TE solutions, with the potential to act as bioactive topical platforms. [ABSTRACT FROM AUTHOR]

Cytostatics are highly toxic pharmaceuticals used in the treatment of cancer. These substances are partially excreted by the human body after administration. The inefficient removal of some cytostatics in urban wastewater treatment plants (WWTPs) allows them to reach surface waters and consequently the aquatic biota. However, information about their occurrence in urban wastewaters is available only for certain active ingredients. A liquid-liquid extraction method coupled to liquid-chromatography-tandem mass spectrometry analysis was developed, allowing the identification and quantification of 14 cytostatics in wastewater samples, avoiding the use of expensive sorbents. Moreover, satisfactory cytostatics' recoveries were achieved when the new method was applied to wastewaters from a Portuguese WWTP: average of (74 ± 21)% for the influents, (83 ± 22)% for secondary effluents, and (94 ± 24)% for tertiary effluents collected after UV treatment, except for imatinib. Doxorubicin, etoposide, megestrol and prednisone were completely eliminated in the first stage of the WWTP treatment (i.e. detected in the influents, but not in the effluents). Bicalutamide, capecitabine, cyclophosphamide, ifosfamide and mycophenolic acid were recalcitrant to UV radiation (i.e. detected in tertiary effluents), ifosfamide being the cytostatic most difficult to be removed (its concentration did not decrease from the entrance to the outlet of the WWTP). The risk at which aquatic organisms might be subjected, due to their exposure to cytostatics' concentrations 10-times lower than those found in the tertiary effluents, was estimated and it was verified that mycophenolic acid may represent a high risk. Although no risk was estimated for the other cytostatics, the risks associated to long-term and synergic exposure should not be ruled out. Unlabelled Image • Miniaturized liquid-liquid extraction is reliable and easy to implement. • 11 (out of 14) cytostatics were detected in wastewater treatment plant influents. • 6 (out of 11) cytostatics were completely degraded in the wastewater treatment plant. • 5 target cytostatics were recalcitrant to ultraviolet radiation • Mycophenolic acid is suspected to induce high risk in aquatic organisms. [ABSTRACT FROM AUTHOR]

The threat of antibiotic resistance to the wellbeing of societies is well established. Urban wastewater treatment plants (UWTPs) are recognised sources for antibiotic resistance dissemination in the environment. Herein a novel cerium-doped zinc oxide (Ce-ZnO) photocatalyst is compared to ZnO and the benchmark TiO2-P25 in the immobilised form on a metallic support, to evaluate a photocatalytic process as a possible tertiary treatment in UWTPs. The catalysts were compared for the removal of two antibiotics, trimethoprim (TMP) and sulfamethoxazole (SMX), and for the inactivation of Escherichia coli (E. coli) strain DH5-Alpha in isotonic sodium chloride solution and of autochthonous bacteria in real secondary wastewater. In real wastewater, E. coli and other coliforms were monitored, as well as the respective fractions resistant to ofloxacin and azithromycin. In parallel, Pseudomonas aeruginosa and the respective sub-population resistant to ofloxacin or ciprofloxacin were also monitored. Photocatalysis with both ZnO and Ce-ZnO was faster than using TiO2-P25 at degrading the antibiotics, with Ce-ZnO the fastest against SMX but slower than undoped ZnO in the removal of TMP. Ce-ZnO catalyst reuse in the immobilised form produced somewhat slower kinetics maintained >50% of the initial activity, even after five cycles of use. Approximately 3 log10 inactivation of E. coli in isotonic sodium chloride water was recorded with reproducible results. In the removal of autochthonous bacteria in real wastewater, Ce-ZnO performed better (more than 2 log values higher) than TiO2-P25. In all cases, E. coli and other coliforms, including their resistant subpopulations, were inactivated at a higher rate than P. aeruginosa. With short reaction times no evidence for enrichment of resistance was observed, yet with extended reaction times low levels of bacterial loads were not further inactivated. Overall, Ce-ZnO is an easy and cheap photocatalyst to produce and immobilise and the one that showed higher activity than the industry standard TiO2-P25 against the tested antibiotics and bacteria, including antibiotic-resistant bacteria. [ABSTRACT FROM AUTHOR]

Abstract Urban wastewater treatment plants (WWTPs) are among the main anthropogenic sources for the release of contaminants of emerging concern (CECs) into the environment, which can result in toxic and adverse effects on aquatic organisms and consequently on humans. Unfortunately, WWTPs are not designed to remove CECs and secondary (e.g., conventional activated sludge process, CAS) and tertiary (such as filtration and disinfection) treatments are not effective in the removal of most CECs entering WWTP. Accordingly, several advanced treatment methods have been investigated for the removal of CECs from wastewater, including consolidated (namely, activated carbon (AC) adsorption, ozonation and membranes) and new (such as advanced oxidation processes (AOPs)) processes/technologies. This review paper gathers the efforts of a group of international experts, members of the NEREUS COST Action ES1403 who for three years have been constructively discussing the state of the art and the best available technologies for the advanced treatment of urban wastewater. In particular, this work critically reviews the papers available in scientific literature on consolidated (ozonation, AC and membranes) and new advanced treatment methods (mainly AOPs) to analyse: (i) their efficiency in the removal of CECs from wastewater, (ii) advantages and drawbacks, (iii) possible obstacles to the application of AOPs, (iv) technological limitations and mid to long-term perspectives for the application of heterogeneous processes, and (v) a technical and economic comparison among the different processes/technologies. Graphical abstract Unlabelled Image Highlights • Adsorption, O 3 , NF and RO membranes filtration can effectively remove CECs. • (Solar driven) AOPs appear competitive for CECs removal from urban wastewater. • When applying O 3 or AOPs ecotoxicological studies should be performed. • Lack of comparative investigations between consolidated and new processes • Conclusive evaluation of the most suitable and cost effective solution/s not yet possible [ABSTRACT FROM AUTHOR]

The effect of different membranes, membrane modules, feed temperatures, flow rates and solute concentrations on the permeate flux and salt rejection in direct contact membrane distillation (DCMD) was first studied with synthetic seawater and compared to distilled water. After optimizing these operating conditions, DCMD was tested with real feed samples, namely river water (RW-R), seawater (SW-R), and a secondary effluent from a municipal wastewater treatment plant (MW-R). The permeate flux achieved with MW-R was significantly lower than those obtained with the other feed samples. Two membrane module configurations (H-cell and W-cell) were then studied using SW-S, spiking diphenhydramine (DP) as model organic pollutant in some experiments. The H-cell performed better in terms of permeate quality for the same volume of permeate collected. A long experiment (500 h) was conducted with SW-R employing a larger H-cell. Severe fouling was observed, but high rejections of ion species (>99%) were recorded together with complete rejections of pharmaceuticals (diclofenac, azithromycin, clarithromycin and erythromycin) detected in SW-R at 9.53–73.53 ng L −1 (detection limits <0.16 ng L −1 ). Colonies of Escherichia coli or enterococci were not detected in 100 mL of permeate (distillate) solution, complying with the European Directive for drinking water. [ABSTRACT FROM AUTHOR]

In the current paper, a new strategy for risk assessment of nanomaterials is described, which builds upon previous project outcomes and is developed within the FP7 NANoREG project. NANoREG has the aim to develop, for the long term, new testing strategies adapted to a high number of nanomaterials where many factors can affect their environmental and health impact. In the proposed risk assessment strategy, approaches for (Quantitative) Structure Activity Relationships ((Q)SARs), grouping and read-across are integrated and expanded to guide the user how to prioritise those nanomaterial applications that may lead to high risks for human health. Furthermore, those aspects of exposure, kinetics and hazard assessment that are most likely to be influenced by the nanospecific properties of the material under assessment are identified. These aspects are summarised in six elements, which play a key role in the strategy: exposure potential, dissolution, nanomaterial transformation, accumulation, genotoxicity and immunotoxicity. With the current approach it is possible to identify those situations where the use of nanospecific grouping, read-across and (Q)SAR tools is likely to become feasible in the future, and to point towards the generation of the type of data that is needed for scientific justification, which may lead to regulatory acceptance of nanospecific applications of these tools. [ABSTRACT FROM AUTHOR]

Photocatalytic ozonation was employed for the first time in continuous mode with TiO 2 -coated glass Raschig rings and light emitting diodes (LEDs) to treat urban wastewater as well as surface water collected from the supply area of a drinking water treatment plant (DWTP). Different levels of contamination and types of contaminants were considered in this work, including chemical priority substances (PSs) and contaminants of emerging concern (CECs), as well as potential human opportunistic antibiotic resistant bacteria and their genes (ARB&ARG). Photocatalytic ozonation was more effective than single ozonation (or even than TiO 2 catalytic ozonation) in the degradation of typical reaction by-products (such as oxalic acid), and more effective than photocatalysis to remove the parent micropollutants determined in urban wastewater. In fact, only fluoxetine, clarithromycin, erythromycin and 17-alpha-ethinylestradiol (EE2) were detected after photocatalytic ozonation, by using solid-phase extraction (SPE) pre-concentration and LC-MS/MS analysis. In surface water, this treatment allowed the removal of all determined micropollutants to levels below the limit of detection (0.01–0.20 ng L −1 ). The efficiency of this process was then assessed based on the capacity to remove different groups of cultivable microorganisms and housekeeping (16S rRNA) and antibiotic resistance or related genes ( intI1, blaTEM , qnrS , sul1 ). Photocatalytic ozonation was observed to efficiently remove microorganisms and ARGs. Although after storage total heterotrophic and ARB (to ciprofloxacin, gentamicin, meropenem), fungi, and the genes 16S rRNA and intI1 , increased to values close to the pre-treatment levels, the ARGs ( blaTEM , qnrS and sul1 ) were reduced to levels below/close to the quantification limit even after 3-days storage of treated surface water or wastewater. Yeast estrogen screen (YES), thiazolyl blue tetrazolium reduction (MTT) and lactate dehydrogenase (LDH) assays were also performed before and after photocatalytic ozonation to evaluate the potential estrogenic activity, the cellular metabolic activity and the cell viability. Compounds with estrogenic effects and significant differences concerning cell viability were not observed in any case. A slight cytotoxicity was only detected for Caco-2 and hCMEC/D3 cell lines after treatment of the urban wastewater, but not for L929 fibroblasts. [ABSTRACT FROM AUTHOR]

Direct photolysis and TiO 2 -photocatalytic degradation of naproxen (NPX) in aqueous solution were studied using a UV lamp and solar irradiation. The degradation of NPX was found to be in accordance with pseudo-first order kinetics, the photocatalytic process being more efficient than photolysis. The NPX removal by photolysis (pH initial 6.5) was 83% after 3 h, with 11% of chemical oxygen demand (COD) reduction, whereas the TiO 2 -UV process led to higher removals of both NPX (98%) and COD (25%). The apparent pseudo-first-order rate constant ( k app ) for NPX degradation by photolysis ranged from 0.0050 min −1 at pH 3.5 to 0.0095 min −1 at pH 6.5, while it was estimated to be 0.0063 min −1 under acidic conditions in photocatalysis, increasing by 4-fold at pH 6.5. Ultra High Performance Liquid chromatography (UHPLC) coupled with a triple quadrupole detector and also a hybrid mass spectrometer which combines the linear ion trap triple quadrupole (LTQ) and OrbiTrap mass analyser, were used to identify NPX degradation products. The main intermediates detected were 1-(6-methoxynaphtalene-2-yl) ethylhydroperoxide, 2-ethyl-6-methoxynaphthalene, 1-(6-methoxynaphtalen-2-yl) ethanol, 1-(6-methoxynaphtalen-2-yl) ethanone and malic acid. Solar photocatalysis of NPX showed COD removals of 33% and 65% after 3 and 4 h of treatment, respectively, and some reduction of acute toxicity, evaluated by the exposure of Eisenia andrei to OECD soils spiked with NPX-treated solutions. [ABSTRACT FROM AUTHOR]