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Antineoplastic drugs are pharmaceuticals that have been raising concerns among the scientific community due to: (i) their increasing prescription in the fight against the disease of the twentieth century (cancer); (ii) their recalcitrance to conventional wastewater treatments; (iii) their poor environmental biodegradability; and (iv) their potential risk to any eukaryotic organism. This emerges the urgency in finding solutions to mitigate the entrance and accumulation of these hazardous chemicals in the environment. Advanced oxidation processes (AOPs) have been taken into consideration to improve the degradation of antineoplastic drugs in wastewater treatment plants (WWTPs), but the formation of by-products that are more toxic or exhibit a different toxicity profile than the parent drug is frequently reported. This work evaluates the performance of a nanofiltration pilot unit, equipped with a Desal 5DK membrane, in the treatment of real WWTP effluents contaminated (without spiking) with eleven pharmaceuticals, five of which were never studied before. Average removals of 68 ± 23% were achieved for the eleven compounds, with decreasing risks from feed to permeate for aquatic organisms from receiving waterbodies (with the exception of cyclophosphamide, for which a high risk was estimated in the permeate). Aditionally, no significative impact on the growth and germination of three different seeds (Lepidium sativum, Sinapis alba, and Sorghum saccharatum) were determined for permeate matrix in comparison to the control. [Display omitted] • Up to 127 ± 20 ng/L (feed), 38 ± 2 ng/L (permeate) and 1512 ± 70 ng/L (retentate). • Average removals of 68 ± 23% were achieved for the eleven pharmaceuticals. • Risk to aquatic organisms was decreased after nanofiltration. • Permeate did not affect the germination/growth of plants compared to control. • Degradation post-treatments are recommended after the nanofiltration process. [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]

After insertion into bone, dental implants may be subjected to tribocorrosive conditions resulting in the release of metallic ions and solid wear debris, which can induce to peri-implant inflammatory reactions accompanied by bone loss, and ultimately implant loosening. Despite the promising ability of TiO 2 nanotubes (NTs) to improve osseointegration and avoid infection-related failures, the understanding of their degradation under the simultaneous action of wear and corrosion (tribocorrosion) is still very limited. This study aims, for the first time, to study the tribocorrosion behavior of bio-functionalized TiO 2 NTs submitted to two-cycle sliding actions, and compare it with conventional TiO 2 NTs. TiO 2 NTs grown by anodization were doped with bioactive elements, namely calcium (Ca), phosphorous (P), and zinc (Zn), through reverse polarization anodization treatments. Characterization techniques such as scanning electron microscopy (SEM), energy dispersive X-ray spectroscopy (EDS) and scanning transmission electron microscopy (STEM), were used to characterize the films. Tribocorrosion tests were carried out in artificial saliva (AS) by applying two cycles of reciprocating sliding actions. The open circuit potential (OCP) was monitored before, during, and after both cycles of sliding, during which the coefficient of friction (COF) was calculated. The resulting wear scars were analyzed by SEM and EDS, and wear volume measurements were performed by 2D profilometry. Finally, the mechanical features of TiO 2 NTs were accessed by nanoindentation. The results show that bio-functionalized TiO 2 NTs display an enhanced tribocorrosion performance, ascribed to the growth of a nano-thick oxide film at Ti/TiO 2 NTs interface, which significantly increased their adhesion strength to the substrate and consequently their hardness. Furthermore, it was discovered that during tribo-electrochemical solicitations, the formation of a P-rich tribofilm takes place, which grants both electrochemical protection and resistance to mechanical wear. This study provides fundamental and new insights for the development of multifunctional TiO 2 NTs with long-term biomechanical stability and improved clinical outcomes. [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 presence of organic pollutants in the aquatic environment, usually found at trace concentrations (i.e., between ng L −1 and μg L −1 or even lower, known as micropollutants), has been highlighted in recent decades as a worldwide environmental concern due to their difficult elimination by conventional water and wastewater treatment processes. The relevant information on constructed wetlands (CWs) and their application for the removal of a specific group of pollutants, 41 organic priority substances/classes of substances (PSs) and 8 certain other substances with environmental quality standards (EQS) listed in Directive 2013/39/EU as well as 17 contaminants of emerging concern (CECs) of the Watch List of Decision 2015/495/EU, is herein reviewed. Studies were found for 24 PSs and 2 other substances with EQS: octylphenol, nonylphenol, perfluorooctane sulfonic acid, di(2-ethylhexyl)phthalate, trichloromethane, dichloromethane, 1,2-dichloroethane, pentachlorobenzene, benzene, polychlorinated dibenzo-p-dioxins, naphthalene, fluoranthene, trifluralin, alachlor, isoproturon, diuron, tributyltin compounds, simazine, atrazine, chlorpyrifos (chlorpyrifos-ethyl), chlorfenvinphos, hexachlorobenzene, pentachlorophenol, endosulfan, dichlorodiphenyltrichloroethane (or DDT) and dieldrin. A few reports were also published for 8 CECs: imidacloprid, erythromycin, clarithromycin, azithromycin, diclofenac, estrone, 17-beta-estradiol and 17-alpha-ethinylestradiol. No references were found for the other 17 PSs, 6 certain other substances with EQS and 9 CECs listed in EU legislation. [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]

Silica@polymer spheres with a core@shell structure were synthesized and thermally annealed at 800 ºC to obtain silica@carbon spheres (SiO 2 @CSs). The silica core was removed by etching with NaOH, hollow carbon spheres (CSs) being obtained. The particle size of SiO 2 @CSs and CSs increased with the ethanol/water (E/W) volumetric ratio (2, 4.5, and 7) employed in the first synthesis step (i.e. , the Stöber's method to obtain silica particles). Moreover, the average diameter of the materials prepared with E/W ratio of 2 was affected by the etching of the SiO 2 core (from 168 to 109 nm), in contrast with those synthesized at higher E/W ratios of 4.5 and 7 (251–245 and 270–284 nm, respectively). The specific surface area (S BET) of the CSs ranged from 271 to 602 m2 g−1, which are more porous than SiO 2 @CSs (S BET in the range 115–144 m2 g−1). Adsorption kinetic and equilibrium studies were carried out with diclofenac and venlafaxine as model organic micropollutants (OMPs). Despite the silica removal was not effective for all the CSs (TGA residue ranging from 3 to 46 wt%), the kinetic studies and the ATR-FTIR spectra confirmed the positive effect of having a hollow core (i.e. , removing the silica core). Equilibrium studies demonstrated that CSs prepared with an E/W ratio of 7 were the best performing material when considering both OMPs. Moreover, these CSs performed well to remove a set of 24 OMPs from wastewater effluents and thus, they are an interesting option for water or wastewater treatment. [Display omitted] • Nanostructured hollow carbon spheres (CSs) with different sizes synthesized. • First study employing CSs for the adsorption of diclofenac and venlafaxine (VFX). • Beneficial role of the hollow core within the CSs was demonstrated. • Best performance in equilibrium tests with the CSs having larger particle size. • Highest VFX adsorption capacity (61.45 mg g-1) among reported carbon materials. [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]

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]

Ozone-based water treatments were investigated to simultaneously remove organic micropollutants (OMPs) and bacteria from surface water samples collected in a river reservoir supplying a drinking water treatment plant. Among the 21 environmentally relevant OMPs selected, 15 were detected at low (< 20) ng L−1 level. Surface water samples were then spiked with these 21 OMPs (100 ng L−1) and the ozone-based treatments were tested with excess of ozone and high hydraulic retention time (HRT: 41 min). Regardless of the treatment applied (O 3 , O 3 /UVA-LEDs, and O 3 /H 2 O 2), removal efficiencies higher than 85% were always obtained for 20 out of 21 OMPs (and lower than 50% for PFOS). Thus, single ozonation was considered the best treatment solution, being afterwards investigated in terms of water disinfection at milder operating conditions (3 mg O 3 L−1 and HRT: 10 min). Under these conditions, the removals of spiked OMPs were also higher than 85% (except for PFOS), whereas bacteria (i.e. , total heterotrophs at 37 and 22 °C, E. coli and enterococci) decreased to values lower than the permissible levels for drinking water, even upon storage for 3-days. However, lower ozone doses (1.5 mg O 3 L−1) could not prevent the regrowth of total heterotrophs incubated at 37 °C, which reached levels five times higher than those recommended. Because drinking water treatments should not only consider OMPs abatement but also microbial inactivation for long periods of time, the results herein obtained point out the importance of using ozone doses capable of accomplish both targets when using single ozonation. [Display omitted] • Ozone-based treatments investigated for surface water intended for consumption. • 20 out of 21 organic micropollutants were removed (>85%) by single ozonation. • PFOS removals were lower than 50% regardless of the treatment process tested. • The treated water had sufficient microbial quality for human consumption. • Ozone doses lower than 3 mg O 3 L−1 are not recommended due to bacteria regrowth. [ABSTRACT FROM AUTHOR]

• DCF and MET are degraded efficiently under visible light, using g-C 3 N 4. • In real water matrices, DCF and MET undergo by indirect photolysis. • DCF had a competitive impact on the removal of MET. • MET had only a slight impact on the degradation of DCF. • Radical and holes play an essential role in the degradation of DCF and MET. In this work, graphite-like carbon nitride (CN) materials were activated with 417 nm light from a LED device for the photocatalytic decomposition of commonly prescribed pharmaceuticals that are recurrent as organic micropollutants (MPs) in environmental waters. The decomposition resistance of diclofenac (DCF) and metoprolol (MET) was investigated by spiking these MPs in different water matrices: ultrapure water, river water, and wastewater. The photochemical stability of both MPs, each constituent ionic species' impact, and the MPs' competitive effect during the photocatalytic treatment were investigated. The target MPs had some photochemical instability under visible light in real water samples, suggesting that the organic matter present on it may act as a photosensitizer and promote these MPs' photodegradation. Besides, competition between the MPs was verified. A noteworthy decrease in the MET kinetic constants was observed when DCF was co-occurring in solution, independently of the water matrix and the initial concentration of the competing MP. By trapping photogenerated holes and radicals with selective scavengers, we found that different ratios of the reactive species are generated during the photocatalytic process, which relies on the presence of each or both MPs. [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]

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]

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 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]

[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]

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]

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]