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Glyphosate is a widely used herbicide, and it is an important environmental pollutant that can have adverse effects on human health. Therefore, remediation and reclamation of contaminated streams and aqueous environments polluted by glyphosate is currently a worldwide priority. Here, we show that the heterogeneous nZVI-Fenton process (nZVI + H2O2; nZVI: nanoscale zero-valent iron) can achieve the effective removal of glyphosate under different operational conditions. Removal of glyphosate can also take place in the presence of excess nZVI, without H2O2, but the high amount of nZVI needed to remove glyphosate from water matrices on its own would make the process very costly. Glyphosate removal via nZVI--Fenton was investigated in the pH range of 3-6, with different H2O2 concentrations and nZVI loadings. We observed significant removal of glyphosate at pH values of 3 and 4; however, due to a loss in efficiency of Fenton systems with increasing pH values, glyphosate removal was no longer effective at pH values of 5 or 6. Glyphosate removal also occurred at pH values of 3 and 4 in tap water, despite the occurrence of several potentially interfering inorganic ions. Relatively low reagent costs, a limited increase in water conductivity (mostly due to pH adjustments before and after treatment), and low iron leaching make nZVI-Fenton treatment at pH 4 a promising technique for eliminating glyphosate from environmental aqueous matrices.
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Depression, either bipolar or unipolar, is a highly prevalent and disabling condition. Even though several treatment options exist for depressed patients, a significant portion of individuals receiving conventional pharmacotherapy fails to achieve and sustain remission. For this reason, there is a strong need for effective alternatives to pharmacotherapy. In this respect, non-invasive brain stimulation (NIBS), including transcranial magnetic stimulation (TMS) and transcranial direct current stimulation (tDCS), have been increasingly investigated in the last two decade as promising treatment strategies for major depression and treatment-resistant depression (TRD). Indeed, due to their safety and tolerability and to the growing evidence on their efficacy, NIBS has been included in international treatment guidelines, having become part of the standard clinical practice. Even though several clinical trials involving NIBS in patients with major depression and TRD have been conducted, literature in specific areas is still marked by some inconsistencies, due to small sample-sizes, lack of multicentre-studies and to the difficulty in comparing different treatment modalities and stimulation protocols. In light of the above, we sought to provide a brief, updated compendium of the latest innovative acquisition for the use of NIBS in the treatment of depression, either unipolar or bipolar, as well as TRD with a specific focus on innovative set-up, devices, target areas, and parameters that may affect the outcome.
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Transtorno Bipolar , Transtorno Depressivo Maior , Estimulação Transcraniana por Corrente Contínua , Humanos , Transtorno Bipolar/terapia , Estimulação Transcraniana por Corrente Contínua/métodos , Estimulação Magnética Transcraniana/métodos , Transtorno Depressivo Maior/terapia , Encéfalo/fisiologiaRESUMO
Over the past decade, biochar (BC) has received significant attention in many environmental applications, including water purification, since it is available as a low-cost by-product of the energetic valorisation of biomass. Biochar has many intrinsic characteristics, including its porous structure, which is similar to that of activated carbon (AC), which is the most widely used sorbent in water treatment. The physicochemical and performance characteristics of BCs are usually non-homogenously investigated, with several studies only evaluating limited parameters, depending on the individual perspective of the author. Within this review, we have taken an innovative approach to critically survey the methodologies that are generally used to characterize BCs and ACs to propose a comprehensive and ready-to-use database of protocols. Discussion about the parameters of chars that are usually correlated with adsorption performance in water purification is proposed, and we will also consider the physicochemical properties of pollutants (i.e., Kow). Uniquely, an adsorption efficiency index BC/AC is presented and discussed, which is accompanied by an economic perspective. According to our survey, non-homogeneous characterization approaches limit the understanding of the correlations between the pollutants to be removed and the physicochemical features of BCs. Moreover, the investigations of BC as an adsorption medium necessitate dedicated parallel studies to compare BC characteristics and performances with those of ACs.
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Carvão Vegetal/química , Purificação da Água/métodos , Água/química , Adsorção , Humanos , Cinética , Poluentes Químicos da Água/químicaRESUMO
Among the advanced oxidation processes (AOPs), the Fenton reaction has attracted much attention in recent years for the treatment of water and wastewater. This review provides insight into a particular variant of the process, where soluble Fe(II) salts are replaced by zero-valent iron (ZVI), and hydrogen peroxide (H2O2) is replaced by persulfate (S2O82-). Heterogeneous Fenton with ZVI has the advantage of minimizing a major problem found with homogeneous Fenton. Indeed, the precipitation of Fe(III) at pH > 4 interferes with the recycling of Fe species and inhibits oxidation in homogeneous Fenton; in contrast, suspended ZVI as iron source is less sensitive to the increase of pH. Moreover, persulfate favors the production of sulfate radicals (SO4â¢-) that are more selective towards pollutant degradation, compared to the hydroxyl radicals (â¢OH) produced in classic, H2O2-based Fenton. Higher selectivity means that degradation of SO4â¢--reactive contaminants is less affected by interfering agents typically found in wastewater; however, the ability of SO4â¢- to oxidize H2O/OH- to â¢OH makes it difficult to obtain conditions where SO4â¢- is the only reactive species. Research results have shown that ZVI-Fenton with persulfate works best at acidic pH, but it is often possible to get reasonable degradation at pH values that are not too far from neutrality. Moreover, inorganic ions that are very common in water and wastewater (Cl-, HCO3-, CO32-, NO3-, NO2-) can sometimes inhibit degradation by scavenging SO4â¢- and/or â¢OH, but in other cases they even enhance the process. Therefore, ZVI-Fenton with persulfate might perform unexpectedly well in some saline waters, although the possible formation of harmful by-products upon oxidation of the anions cannot be ruled out.
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BACKGROUND: The presence of biogenic amines (BAs) fermented food is well known. They may affect food quality, posing health risks. In this work, four typical Italian cheeses, exported worldwide, were analyzed to determine the possible presence of BAs. The cheese samples were analyzed untreated and having been subjected to common or incorrect consumer handling (domestic grating, unrefrigerated storage). RESULTS: A chromatographic-amperometric method was developed and validated. Extraction of BAs was performed by the addition of eluent, determining matrix effect and recovery of biogenic amines directly within the cheeses. Biogenic amines were present in the range of 0.019-0.044 g kg-1 , well below the current EU limit. Home-manipulation confirmed recontamination of the cheese. The contents of BAs were correlated with the main processing parameters and with the nutritional properties of the four cheeses through the multivariate statistical analysis (principal component analysis). This is believed to be the first study that presents these correlations. CONCLUSION: This study highlights correlations among BAs and carbohydrates, and anticorrelations with pH and, to a lesser extent, with moisture. Interestingly, BAs are correlated with fat content. This correlation was confirmed by a new principal component analysis performed on our data set with additional data from the literature. © 2019 Society of Chemical Industry.
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Aminas Biogênicas/análise , Queijo/análise , Manipulação de Alimentos/métodos , Valor Nutritivo , Cromatografia/métodos , Carboidratos da Dieta/análise , Gorduras na Dieta/análise , Proteínas Alimentares/análise , Fermentação , Armazenamento de Alimentos/métodos , Concentração de Íons de Hidrogênio , ItáliaRESUMO
INTRODUCTION: Paliperidone Palmitate is the only antipsychotic that has been developed in three different intramuscular long-acting injectable (LAI) dosing regimen: monthly (PP1M), quarterly (PP3M), and from 2020 also twice-yearly (PP6M). The latter was approved for the maintenance treatment of adults with schizophrenia and clinically stabilized with PP1M or PP3M. AREAS COVERED: Data from studies evaluating efficacy in the maintenance treatment of schizophrenia with PP6M are reviewed. Since no post-marketing safety studies are currently available, data from spontaneous reporting system databases, FAERS and Eudravigilance, are analyzed and the reported treatment-emergent adverse events of PP6M are discussed. EXPERT OPINION: The efficacy of PP6M is comparable to that of PP3M in terms of relapses prevention in patients with schizophrenia previously stabilized on PP3M or PP1M. Also, the maintenance of clinical efficacy in the long term has been demonstrated. Data from pharmacovigilance analyses, as well as from phase 3 studies, show that PP6M is generally well tolerated, consistently with PP3M safety data. PP6M allows a longer dosing interval than any other LAI antipsychotics, potentially reducing nonadherence and disease relapses. In future, an increase in the prescription rates of PP6M is expected and real-world efficacy and tolerability studies will be conducted.
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Antipsicóticos , Esquizofrenia , Adulto , Humanos , Palmitato de Paliperidona/uso terapêutico , Palmitato de Paliperidona/efeitos adversos , Esquizofrenia/tratamento farmacológico , Resultado do Tratamento , RecidivaRESUMO
European and national waste directives prioritize recycling of wastes, as well as material and energy recovery from wastes themselves. Bio-waste fraction can be converted into new resources whose quality is strictly dependent upon that of waste feedstock. Methods to evaluate the contamination from organic micropollutants in bio-waste are rarely investigated. The aim of this work was to develop an innovative analytical method for the extraction and quantification of 16 polycyclic aromatic hydrocarbons (PAHs) and 14 polychlorinated biphenyls (PCBs, including dioxin-like compounds) in bio-waste. Through a full-factorial experimental design, a microwave-assisted extraction technique was optimized to extract the thirty targeted micropollutants, studying the effect of cyclohexane and dichloromethane as extraction solvents with or without acetone, and of extraction temperature. Purification of the extract was obtained by a silica-based solid-phase extraction cartridge, followed by a sulfuric acid treatment. The analysis was carried out by gas chromatography coupled with mass spectrometry. The optimized method, validated directly in the bio-waste matrix fortified with isotopically marked surrogates, is characterized by good extraction recoveries, included within 47 and 106% (relative standard deviations <10%), by satisfactory intra-day (<1.1%) and inter-day (<9.3%) precision, and by low matrix effect (<17%), despite the complexity of the matrix. The optimized procedure, applied to the analysis of PAHs and PCBs in a bio-waste sample collected from a local anaerobic digestion and composting plant, showed a total PAHs content of 562 µg/kg. As regards PCBs, the dioxin-like congener PCB 118 was the only compound quantified (25 ± 6 µg kg-1).
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Bifenilos Policlorados , Hidrocarbonetos Policíclicos Aromáticos , Cromatografia Gasosa-Espectrometria de Massas/métodos , Micro-Ondas , Bifenilos Policlorados/análise , Hidrocarbonetos Policíclicos Aromáticos/análise , Extração em Fase Sólida , Resíduos Sólidos/análiseRESUMO
Seven biochars (BCs) obtained from pyrolysis or gasification of different vegetal feedstocks were thoroughly characterized in comparison with three commercial activated carbons (ACs) routinely used in drinking water treatment plants. BCs and ACs characterization included the determinations of ash, iodine and methylene blue adsorption indexes, and the release of metals and polycyclic aromatic hydrocarbons, which were performed according to international standards applied for adsorption media to be used in drinking waters. Total specific surface area, micropore and mesopore specific surface area, pH of the point of zero charge, and the release of polychlorinated biphenyls were also determined in all chars. Principal component analysis and cluster analysis were performed in order to summarize the complex set of information deriving from the aforementioned characterizations, highlighting the BC most similar (BC6 from high temperature gasification of woody biomass) and most different (BC7 from low-temperature pyrolysis of corn cob) from ACs. These BCs were studied for their adsorption in ultrapure water towards diiodoacetic acid (an emergent disinfection by-product), benzene, and 1.2-dichlorobenzene, in comparison with ACs, and results obtained were fitted by linearized Freundlich equation. Overall, BC6 showed higher sorption performances compared to BC7, even though both BCs were less performing sorbents than ACs. However, the sorption properties of BCs were maintained also in real water samples collected from drinking water treatment plants.
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Poluentes Ambientais , Purificação da Água , Carvão Vegetal , FiltraçãoRESUMO
In the analysis of contaminants in food products, sample preparation is performed by proper adsorbents, whose choice is crucial to eliminate matrix interference. In this work we modified SBA-15 adsorbents by functionalization with (3-aminopropyl)-triethoxysilane (SBA-15-APTES) and N-[3-(trimethoxysilyl)propyl]aniline (SBA-15-AN) aiming to use them for the first time in the clean-up step of a QuEChERS (quick, easy, cheap, effective, rugged and safe) extraction of micropollutants from strawberry, a sugar rich fruit. After physico-chemical characterization by nitrogen adsorption, infrared spectroscopy and thermogravimetric analysis, the adsorption capabilities of SBA-15 sorbents and possible interaction mechanisms were studied at different pH (2.1-8.5) for glucose, sucrose and fructose at concentrations characteristic of those found in strawberries. The performance of the two SBA-15 sorbents was compared with that of commercial PSA (primary secondary amine), usually proposed in QuEChERS protocols. Both SBA-15 materials exhibit up to 30% higher adsorption than PSA, suggesting their possible QuEChERS application. Synthesized SBA-15 adsorbents were hence used as innovative dispersive sorbents in the QuEChERS extractions of 13 PAHs and 14 PCBs from strawberry. For PCBs, SBA-15-AN provides better matrix removal than PSA and comparable extraction recoveries around 90%. For PAHs, the use of SBA-15-AN has the advantage of lower relative standard deviation (7%) than PSA (19%).
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Poluentes Ambientais/análise , Dióxido de Silício/química , Extração em Fase Sólida/métodos , Adsorção , Fragaria/química , Frutas/química , Bifenilos Policlorados/análise , Hidrocarbonetos Policíclicos Aromáticos/análiseRESUMO
BACKGROUND: Domestic and industrial wastewater can be introduced in a reuse chain for irrigation purposes. OBJECTIVE: In this paper, we developed analytical procedures for the extraction of polycyclic aromatic hydrocarbons (PAHs) and polychlorinated biphenyls (PCBs) along a wastewater reuse chain for irrigation purposes. Besides urban wastewaters, olive mill wastewater (OMWW) was considered as a potential water source. Wastewaters were purified by different treatments (urban wastewater plants, pilot-activated sludge, and constructed wetland) and used for the irrigation of olive trees. Suitable extraction procedures were used to analyze treated and untreated wastewaters, soils, and postirrigation leachates. RESULTS: For wastewater and leachate samples, the optimized reverse-phase solid-phase extraction (SPE) provided recoveries up to 79%. For OMWW, the SPE procedure was preceded by a normal-phase purification stage with silica gel for the removal of polyphenols, which were as high as 8.7 g/L. After optimization, extraction recoveries in blank solutions were in the range 20-67% and moderately reduced (10-38%) in OMWW as a result of the matrix effect (ME; -10/-60%) ascribed to the very high value of chemical oxygen demand (264 g/L). LODs of the method were below 1.1 µg/L (PAHs) and 3.2 µg/L (PCBs) using GC-MS analysis. For soil samples of different compositions, microwave-assisted extraction (MAE) provided better extraction recoveries and reproducibility than the more common quick, easy, cheap, effective, rugged, and safe approach, which was affected by a high ME. The LODs of the MAE/GC-MS method were below 4.9 µg/kg (PAHs) and 12.3 µg/kg (PCBs). CONCLUSIONS: The analytical procedures developed are a valuable tool to quantify the possible propagation of residual contamination from PAHs/PCBs with irrigation along the wastewater reuse chain.
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Olea , Bifenilos Policlorados , Hidrocarbonetos Policíclicos Aromáticos , Irrigação Agrícola , Bifenilos Policlorados/análise , Hidrocarbonetos Policíclicos Aromáticos/análise , Reprodutibilidade dos Testes , Águas ResiduáriasRESUMO
According to the recent proposal released by the European Commission for the revision of the 98/83/EC Directive, water suppliers will be requested to monitor the nine bromine- and chlorine congeners of haloacetic acids, HAAs, as well as the oxyhalides chlorite and chlorate, as disinfection by-products (DBPs) originated during the potabilization process. In this work, we propose a direct-injection method based on ion chromatography and mass spectrometric detection for the determination of the mentioned DBPs as well as bromate (already included in the 98/83/EC), implemented also for the following emerging HAAs monoiodo-, chloroiodo- and diiodo-acetic acids. The method was optimized to include the fifteen compounds in the same analytical run, tuning the chromatographic (column and gradient) and detection conditions (suppression current, transitions, RF lens settings and collision energies). To avoid matrix effect and to manage the instrumental conditions, optimization was performed directly in drinking water matrix. The method quantitation limits satisfy the new limits imposed by the future directive and range from 0.08⯵g/L (monobromoacetic acid) to 0.34⯵g/L (trichloroacetic acid). The performance of the method was checked along different strategic sampling points of three potabilization plants serving the city of Turin (Italy), including intermediate treatments and finished waters. Recovery was checked according to the ±30% limit of acceptability set by EPA regulations. The effect of disproportionate concentrations of chlorite and chlorate in respect to HAAs on HAA signals was studied; this aspect is underestimated in literature. The method is routinely applied by the potabilization plant of the city of Turin to confirm the effectiveness of all control measures in abstraction, treatment, distribution and storage. This study represents the first example in Italy of development and use of a cutting-edge technique for HAAs analysis along the potabilization processes.
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Cromatografia , Desinfecção , Água Potável/análise , Espectrometria de Massas em Tandem , Poluentes Químicos da Água/análise , Acetatos/análise , Bromatos/análise , Cloretos/análise , Cloro/análise , Cidades , Água Potável/normas , Itália , Abastecimento de Água/normasRESUMO
PURPOSE: To date, the available data on the relationship between the use of selective serotonin reuptake inhibitors (SSRIs) or the serotonin and norepinephrine reuptake inhibitor (SNRI) venlafaxine and postpartum hemorrhage (PPH) are conflicting and have not been extensively investigated, especially in terms of plasma drug concentrations. We performed data mining of antidepressant-induced PPH reported to the US Food and Drug Administration's Adverse Event Reporting System database, to assess the strength of the potential association between antidepressant pharmacotherapy and PPH in pregnant women. Concurrently, we carried out a descriptive observational population (pregnant women) analysis of the correlation between the plasma concentrations of SSRIs/SNRIs used during pregnancy and the extent of bleeding at delivery. METHODS: A disproportionality analysis of individual case study reports of PPH associated with SSRIs or venlafaxine in pregnant women was performed. Reporting odds ratio was used as a measure of disproportionality analysis. Pregnant women treated with an SSRI or SNRI (venlafaxine) for depressive or anxiety disorder and who consented to plasma drug concentration monitoring at the time of delivery were recruited. Plasma drug concentration assay was performed according to validated LC-MS/MS. Based on plasma drug concentrations, patients were classified into 1 of 2 groups, in therapeutic range or below therapeutic range for the drug administered, in accordance with the Arbeitsgemeinschaft für Neuropsychopharmakologie und Pharmakopsychiatrie guideline, and correlations with blood loss were identified, with PPH defined as a blood loss of >500 mL. FINDINGS: Only 43 Individual Case Safety Reports (ICSRs) reported at least one SSRIs or venlafaxine as suspect drug in 14 years (database analyses). Forty-three women were enrolled in the study population (observational study). In 24 patients (55.8%) the plasma drug concentration was below the therapeutic threshold. Unexpectedly, the mean blood loss in the below-range group was significantly higher than that in the in-range group. PPH occurred in 30% of women: in 9.3% and in 20.7% of patients in the in-range and below-range groups, respectively. IMPLICATIONS: Although preliminary, these data indicate a rather good tolerability profile of SSRIs/SNRIs regarding postpartum bleeding. Moreover, they suggest that keeping the plasma levels of SSRIs/SNRIs low as a precautionary measure does not reduce postpartum bleeding, which was higher in the below-range group. The findings from this study suggest that the use of therapeutic drug monitoring in pregnancy, a period in which multiple variables affect drug metabolism, may allow for better treatment customization, with subsequent advantages in terms of tolerability and efficacy of treatment.
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Antidepressivos/uso terapêutico , Hemorragia Pós-Parto/epidemiologia , Inibidores Seletivos de Recaptação de Serotonina/uso terapêutico , Inibidores da Recaptação de Serotonina e Norepinefrina/uso terapêutico , Adolescente , Adulto , Antidepressivos/sangue , Bases de Dados Factuais , Feminino , Humanos , Pessoa de Meia-Idade , Razão de Chances , Período Pós-Parto , Gravidez , Inibidores Seletivos de Recaptação de Serotonina/sangue , Inibidores da Recaptação de Serotonina e Norepinefrina/sangue , Adulto JovemRESUMO
The presence of residual color in treated textile wastewater above the regulation limits is still a critical issue in many textile districts. Innovative, polymer-derived ceramics of the Si-C-O system were here synthesized in order to obtain porous nanocomposite materials where a free carbon phase is dispersed into a silicon carbide/silicon oxycarbide network. The sorbents were comprehensively characterized for the removal of two model water-soluble dyes (i.e., the cation methylene blue and the zwitterion rhodamine B). Adsorption is very rapid and controlled by intra-particle and/or film diffusion, depending on dye concentration. Among the nanocomposites studied, the SiOC aerogel (total capacity about 45 mg/g, is easily regenerated under mild treatment (250 °C, 2 h). Adsorption of dyes is not affected by the matrix composition: removals of 150 mg/L methylene blue from river water and simulated textile wastewater with high content of metal ions (2-50 mg/L) and chemical oxygen demand (800 mg/L) were higher than 92% and quantitative for a dye concentration of 1 mg/L.