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In this study, the concentration probability distributions of 82 pharmaceutical compounds detected in the effluents of 179 European wastewater treatment plants were computed and inserted into a multimedia fate model. The comparative ecotoxicological impact of the direct emission of these compounds from wastewater treatment plants on freshwater ecosystems, based on a potentially affected fraction (PAF) of species approach, was assessed to rank compounds based on priority. As many pharmaceuticals are acids or bases, the multimedia fate model accounts for regressions to estimate pH-dependent fate parameters. An uncertainty analysis was performed by means of Monte Carlo analysis, which included the uncertainty of fate and ecotoxicity model input variables, as well as the spatial variability of landscape characteristics on the European continental scale. Several pharmaceutical compounds were identified as being of greatest concern, including 7 analgesics/anti-inflammatories, 3 β-blockers, 3 psychiatric drugs, and 1 each of 6 other therapeutic classes. The fate and impact modelling relied extensively on estimated data, given that most of these compounds have little or no experimental fate or ecotoxicity data available, as well as a limited reported occurrence in effluents. The contribution of estimated model input variables to the variance of freshwater ecotoxicity impact, as well as the lack of experimental abiotic degradation data for most compounds, helped in establishing priorities for further testing. Generally, the effluent concentration and the ecotoxicity effect factor were the model input variables with the most significant effect on the uncertainty of output results. [ABSTRACT FROM AUTHOR]

Abstract The removal efficiency of pharmaceuticals in wastewater treatment plants (WWTPs) is variable and some of these compounds pass these plants almost intact and others presenting a removal efficiency close to 100%. Their incomplete removal results in a continuous discharge of pharmaceuticals into the environment. To assess the profile of contamination of influents and effluents over a day, a set of 83 pharmaceuticals were evaluated hourly in a WWTP in Leiria, Portugal. The composite samples of the influent and effluent were also collected. Concentrations varied from 1 in WWTP influents, and carbamazepine, fluoxetine, sertraline the pharmaceuticals with an RQ > 1 in WWTP effluents. Graphical abstract Unlabelled Image Highlights • Hourly variation of 83 pharmaceuticals in WWTP influent and effluent is presented. • Pharmaceuticals belonging to different therapeutic classes were analysed. • Some pharmaceuticals were detected in the influents in the μg/L range. • The importance of the determination of metabolites and transformation products is highlighted. [ABSTRACT FROM AUTHOR]

The contamination of soils is a global environmental problem that urges an increased effort to recover polluted sites. In Europe, there are an estimated 20,000 polluted sites that need to be remediated and around 350,000 sites that are classified as potentially contaminated by the European Environment Agency (EEA). Remediation is a part of the solution to this problem, requiring the most innovative and sustainable technologies. In this context, the use of zero valent iron nanoparticles (nZVI) is a promising, low cost and efficient technology for the remediation of soil and groundwater contaminated with a wide range of organic and inorganic pollutants. Among the nZVIs, the ones produced using Green synthesis methods (green nZVIs (gnZVI)) using natural extracts, such as green tea, are increasingly considered an alternative technology for the future. However, there are issues related to the application of gnZVI in soil that are still not fully understood, requiring further research, among these is the study of their transport in soils. Therefore, this work aims to study the transport of gnZVIs in sandy soils under diverse conditions such as soil particle size, soil saturation level and injection sequence. Several experiments were performed in an acrylic column with two sandy soils with different particle sizes (between 0.5 and 1.0 mm and higher than 1.0 mm), using two distinct water saturation conditions (saturated and dry) and four injection sequences. After these tests the distribution of the gnZVI along the soil column was determined by atomic absorption spectroscopy. This work allowed concluding that the injection sequence might be one of the most important factors influencing the rate of nZVI dispersion through a sandy column. According to the results it was possible to propose, for distinct types of contamination (deep, superficial, hot spot or dispersed), the most appropriate injection sequence. [ABSTRACT FROM AUTHOR]

Since annually a high amount of wastes is produced in vine pruning, the aim of this study was to evaluate the potential of vine shoots from two Portuguese grape varieties ( Touriga Nacional - TN and Tinta Roriz - TR) to be used as a natural source of phenolic compounds. To reach this goal, three techniques were explored, namely microwave-assisted extraction (MAE), subcritical water extraction (SWE) and conventional extraction (CE). The phenolic composition of the extracts, antioxidant and biological activities were evaluated by spectrophotometry and chromatography. MAE and SWE produced the highest concentrated extracts. TR vine shoot variety had the highest antioxidant activity and total phenolic (32.1 ± 0.9 mg gallic acid equivalents/g dry sample), as well as flavonoid content (18.7 ± 1.2 mg epicatechin equivalents/g dry sample). For the first time, the biological activity of the vine shoot extracts was tested. Results demonstrated that all of them had antimicrobial potential against different bacteria and yeasts, and the ability of inhibiting α-amylase and acetylcholinesterase enzymes, with MAE TR extracts being the most efficient. HPLC analysis enabled the identification of different phenolic compounds, with gallic acid, catechin, myricetin and kaempferol-3- O -rutinoside being the main contributors to the phenolic composition. Portuguese vine shoot wastes could serve as easily accessible source of natural antioxidants for the food or pharmaceutical industries. [ABSTRACT FROM AUTHOR]

Pyrethroid pesticides residues have been frequently detected in soils and have been recognized to contribute to soil toxicity. The phytotoxic impact of pesticides was evaluated in Cucumis sativus ( C. sativus ) seeds. Percentage of seed germination, root elongation, shoot length and leaf length were considered as endpoints to assess the possible acute phytotoxicity of soil by the exposure to pyrethroid pesticides (cypermethrin, deltamethrin and cyhalothrin) and its metabolite phenoxybenzoic acid (3-PBA), in a concentration range between 50 and 500 μg kg − 1 . For germination percentage, it was only observed a negative impact when seeds were exposed to the metabolite. Cypermethrin showed impact in the three studied endpoints of seed development, while deltamethrin merely affected the root length. Concerning pigments content, it can be said that chlorophylls and total carotenoids median values increased for cypermethrin and deltamethrin. This increase was more pronounced to deltamethrin in joint effect with the organic solvent dimethyl sulphoxide (DMSO). When exposed to cyhalothrin and 3-PBA, no statistically significant differences were observed for C. sativus seeds to all the assessed endpoints of seed development and the investigated pigments content. This research brings new data concerning the relative sensitivity of C. sativus seeds to pyrethroids pesticides commonly found in agricultural facilities, as well as critical understanding and development of using C. sativus for phytotoxicity assessments efforts for pesticide exposures. [ABSTRACT FROM AUTHOR]

This work aims to characterize personal exposure of firefighters to polycyclic aromatic hydrocarbons (PAHs) in non-fire work environments (fire stations), and assesses the respective risks. Eighteen PAHs (16 considered by USEPA as priority pollutants, dibenzo[ a , l ]pyrene and benzo[ j ]fluoranthene) were monitored in breathing zones of workers at five Portuguese fire stations during a normal shift. The obtained levels of PAHs fulfilled all existent occupational exposure limits as well as air quality guidelines with total concentrations (ΣPAHs) in range of 46.8–155 ng m − 3 . Light compounds (2–3 rings) were the most predominant congeners (74–96% of ΣPAHs) whereas PAHs with 5–6 rings accounted 3–9% of ΣPAHs. Fuel and biomass combustions, vehicular traffic emissions, and use of lubricant oils were identified as the main sources of PAHs exposure at the studied fire corporations. Incremental lifetime cancer risks were below the recommend USEPA guideline of 10 − 6 and thus negligible for all the studied subjects, but WHO health–based guideline level of 10 − 5 was exceeded (9–44 times) at all fire corporations. These results thus show that even during non-fire situations firefighters are exposed to PAHs at levels that may promote some adverse health outcomes; therefore the respective occupational exposures to these compounds should be carefully controlled. [ABSTRACT FROM AUTHOR]

Although polycyclic aromatic hydrocarbons (PAHs) are priority air pollutants that strongly affect human health, information concerning the indoor exposures is still limited. This study characterized PAH levels in primary schools and evaluated risk for the respective students (aged 8–10 years) in comparison with school personnel. During January–April 2014, eighteen particulate–bound (PM 2.5 ) PAHs (16 USEPA priority compounds, dibenzo[ a , l ]pyrene, benzo[ j ]fluoranthene) were collected (indoors and outdoors) at ten primary urban schools in Portugal. Total mean concentrations (Σ PAHs ) ranged 2.8–54 ng m − 3 in indoor air, whereas corresponding outdoor levels were 7.1–48 ng m − 3 . Indoor/outdoor ratios of lighter congeners (2–3 aromatic rings) demonstrated a contribution from indoor origin while heavier PAHs (4–6 aromatic rings) originated mostly from infiltration of ambient air indoors; traffic (both from diesel and gasoline fuelled vehicles) was the predominant source of indoor PAHs. Total cancer risk of 8–10 years old children exceeded (up to 22 times) USEPA recommended guideline of 10 − 6 , and 7–87 times WHO health–based threshold of 10 − 5 . Risk due to indoor exposure in schools was 2–10 times higher than outdoors, mainly because of the higher amount of time that students spent indoors. [ABSTRACT FROM AUTHOR]

The occurrence of 33 pharmaceuticals and metabolites was evaluated along the Lis river and in the influents and effluents of two wastewater treatment plants (WWTPs) located along the river. Results indicate that pharmaceuticals, such as ibuprofen, ketoprofen, carbamazepine and fluoxetine, and the metabolite salicylic acid are widespread along the Lis river, showing 100% of detection frequency, at levels up to 1.3 μg L –1 . The number of molecules detected increased along the river, with 11 molecules in the source, 15 upstream WWTP 1, 16 downstream WWTP 1 and upstream WWTP 2 and 19 downstream WWTP 2. The highest concentrations were often found downstream near the river mouth. Different possible sources of contamination of the Lis river were identified, namely WWTP effluents, untreated wastewaters and livestock production. Nevertheless, the discharge of WWTP effluents appeared to be the most pronounced, given that, in general, it was noticed an increase in the concentration of pharmaceuticals downstream of the WWTPs. WWTP effluents contributed with a total mass load of pharmaceuticals into the Lis river between 470 and 2317 mg/d/1000 inhabitants. Non-steroidal anti-inflammatory drugs/analgesics were the therapeutic group with a high contribution to the total mass load of pharmaceuticals entering the Lis river, followed by psychiatric drugs and antibiotics. No seasonal variation was observed for the detected concentrations of pharmaceuticals. At the levels detected in the Lis river, sulfamethoxazole, clarithromycin, azithromycin and ibuprofen showed to have potential risk for aquatic organisms. These findings show that further studies embracing different environmental compartments (water, sediment and biota) are needed, in order to evaluate the partition/distribution of pharmaceuticals, their metabolites and transformation products in the environment as well as to predict their possible impact to non-target organisms and, in a last instance, to human health. [ABSTRACT FROM AUTHOR]

The occurrence of seven pharmaceuticals and two metabolites belonging to non-steroidal anti-inflammatory drugs and analgesics therapeutic classes was studied in seawaters. A total of 101 samples covering fourteen beaches and five cities were evaluated in order to assess the spatial distribution of pharmaceuticals among north Portuguese coast. Seawaters were selected in order to embrace different bathing water quality (excellent, good and sufficient). Acetaminophen, ketoprofen and the metabolite hydroxyibuprofen were detected in all the seawater samples at maximum concentrations of 584, 89.7 and 287 ng L − 1 , respectively. Carboxyibuprofen had the highest seawater concentration (1227 ng L − 1 ). The temporal distribution of the selected pharmaceuticals during the bathing season showed that, in general, higher concentrations were detected in August and September. The environmental risk posed by the pharmaceuticals detected in seawaters towards different trophic levels (fish, daphnids and algae) was also assessed. Only diclofenac showed hazard quotients above one for fish, representing a potential risk for aquatic organisms. These results were observed in seawaters classified as excellent bathing water. Additional data is needed in order to support the identification and prioritization of risks posed by pharmaceuticals in marine environment. [ABSTRACT FROM AUTHOR]

Abstract: Among organic pollutants existing in coastal areas, polycyclic aromatic hydrocarbons (PAHs) are of great concern due to their ubiquity and carcinogenic potential. The aim of this study was to evaluate the seasonal patterns of PAHs in the digestive gland and arm of the common octopus (Octopus vulgaris) from the Northwest Atlantic Portuguese coast. In the different seasons, 18 PAHs were determined and the detoxification capacity of the species was evaluated. Ethoxyresorufin O-deethylase (EROD) and ethoxycoumarin O-deethylase (ECOD) activities were measured to assess phase I biotransformation capacity. Individual PAH ratios were used for major source (pyrolytic/petrogenic) analysis. Risks for human consumption were determined by the total toxicity equivalence approach. Generally, low levels of PAHs were detected in the digestive gland and in the arm of octopus, with a predominance of low molecular over high molecular weight compounds. PAHs exhibited seasonality in the concentrations detected and in their main emission sources. In the digestive gland, the highest total PAH levels were observed in autumn possibly related to fat availability in the ecosystem and food intake. The lack of PAH elimination observed in the digestive gland after captivity could be possibly associated to a low biotransformation capacity, consistent with the negligible/undetected levels of EROD and ECOD activity in the different seasons. The emission sources of PAHs found in the digestive gland varied from a petrogenic profile observed in winter to a pyrolytic pattern in spring. In the arm, the highest PAH contents were observed in June; nevertheless, levels were always below the regulatory limits established for food consumption. The carcinogenic potential calculated for all the sampling periods in the arm were markedly lower than the ones found in various aquatic species from different marine environments. The results presented in this study give relevant baseline data for environmental monitoring of organic pollution in coastal areas. [Copyright &y& Elsevier]

Abstract: The impact of effluent wastewaters from four different hospitals: a university (1456 beds), a general (350 beds), a pediatric (110 beds) and a maternity hospital (96 beds), which are conveyed to the same wastewater treatment plant (WWTP), was evaluated in the receiving urban wastewaters. The occurrence of 78 pharmaceuticals belonging to several therapeutic classes was assessed in hospital effluents and WWTP wastewaters (influent and effluent) as well as the contribution of each hospital in WWTP influent in terms of pharmaceutical load. Results indicate that pharmaceuticals are widespread pollutants in both hospital and urban wastewaters. The contribution of hospitals to the input of pharmaceuticals in urban wastewaters widely varies, according to their dimension. The estimated total mass loadings were 306gd−1 for the university hospital, 155gd−1 for the general one, 14gd−1 for the pediatric hospital and 1.5gd−1 for the maternity hospital, showing that the biggest hospitals have a greater contribution to the total mass load of pharmaceuticals. Furthermore, analysis of individual contributions of each therapeutic group showed that NSAIDs, analgesics and antibiotics are among the groups with the highest inputs. Removal efficiency can go from over 90% for pharmaceuticals like acetaminophen and ibuprofen to not removal for β-blockers and salbutamol. Total mass load of pharmaceuticals into receiving surface waters was estimated between 5 and 14g/d/1000 inhabitants. Finally, the environmental risk posed by pharmaceuticals detected in hospital and WWTP effluents was assessed by means of hazard quotients toward different trophic levels (algae, daphnids and fish). Several pharmaceuticals present in the different matrices were identified as potentially hazardous to aquatic organisms, showing that especial attention should be paid to antibiotics such as ciprofloxacin, ofloxacin, sulfamethoxazole, azithromycin and clarithromycin, since their hazard quotients in WWTP effluent revealed that they could pose an ecotoxicological risk to algae. [Copyright &y& Elsevier]

Abstract: Ibuprofen is one of the most used active pharmaceutical ingredients worldwide. A new method for the analysis of ibuprofen and its metabolites, hydroxyibuprofen and carboxyibuprofen, in soils is presented. The extraction of these compounds from the soil matrices was performed by using a modified quick, easy, cheap, effective, rugged, and safe (QuEChERS) method. The method involves a single extraction of the investigated compounds with purified water (acidified at pH 2.5 with hydrochloric acid), and a slow and continuous addition of the QuEChERS content, followed by the addition of acidified acetonitrile (1% acetic acid), prior to the determination by liquid chromatography coupled with fluorescence detection (LC–FLD). Validation studies were carried out using soil samples with a range of organic carbon contents. Recoveries of the fortified samples ranged from 79.5% to 101%. Relative standard deviations for all matrix–compound combinations did not exceed 3%. The method quantification limits were ≤22.4μgkg−1 in all cases. The developed method was applied to the analysis of sixteen real samples. [Copyright &y& Elsevier]

Abstract: Metals are ubiquitous in the environment and accumulate in aquatic organisms and are known for their ability to enhance the production of reactive oxygen species (ROS). In aquatic species, oxidative stress mechanisms have been studied by measuring antioxidant enzyme activities and oxidative damages in tissues. The aim of this study was to apply and validate a set of oxidative stress biomarkers and correlate responses with metal contents in tissues of common octopus (Octopus vulgaris). Antioxidant enzyme activity (catalase — CAT, superoxide dismutase — SOD and glutathione S-transferases — GST), oxidative damages (lipid peroxidation — LPO and protein carbonyl content — PCO) and metal content (Cu, Zn, Pb, Cd and As) in the digestive gland and arm of octopus, collected in the NW Portuguese coast in different periods, were assessed after capture and after 14days in captivity. CAT and SOD activities were highly responsive to fluctuations in metal concentrations and able to reduce oxidative damage, LPO and PCO in the digestive gland. CAT activity was also positively correlated with SOD and GST activities, which emphasizes that the three enzymes respond in a coordinated way to metal induced oxidative stress. Our results validate the use of oxidative stress biomarkers to assess metal pollution effects in this ecological and commercial relevant species. Moreover, octopus seems to have the ability to control oxidative damage by triggering an antioxidant enzyme coordinated response in the digestive gland. [Copyright &y& Elsevier]