NATHALIA FONSECA BOIANI

NATHALIA FONSECA BOIANI

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Toxicity removal of pharmaceuticals, fluoxetine and caffeine, by electron beam irradiation
2023 - BOIANI, NATHALIA F.; REDIGOLO, MARCELO M.; CALVO, WILSON A.; TOMINAGA, FLAVIO K.; BORRELY, SUELI I.
The wide use of pharmaceuticals and water scarcity are associated to increasing levels of pharmaceutical compounds discharged into water and wastewater worldwide, affecting relevant ecological services, including biodegradation. However, water pollution has also encouraged studies applying advanced oxidative processes (AOP) in organic pollutant degradation. Among AOPs, ionizing radiation has been proven an effective technology for organic compound removal from waters and wastewater. The objective of this study was to assess Electron Beam (EB) irradiation in the degradation of caffeine and fluoxetine and their binary mixture in pure aqueous solutions. The degradation of these pharmaceuticals was evaluated by GC/MS analyses. The degradation dose response was higher for the caffeine and fluoxetine mixture (1:1) at 2.5 kGy. This dose led to decreased toxicity towards Daphnia similis for both the fluoxetine + caffeine mixture and the isolated fluoxetine solution, but not for the isolated caffeine. On the other hand, Vibrio fischeri exposure for 15 min indicated toxicity removal for the entire pharmaceuticals sample set and radiation dose. Fluoxetine was the most toxic pharmaceutical, followed by the binary mixture. Thus, we suggest ecopharmacovigilance, where attention should be paid to the increasing amount of pharmaceuticals, caffeine and fluoxetine detected in water.
Avaliação da toxicidade aguda e dos efeitos da irradiação com feixe de elétrons em misturas de compostos farmacêuticos
2022 - BOIANI, NATHALIA F.
Atualmente uma vasta gama de contaminantes vêm sendo detectados no meio hídrico, os produtos farmacêuticos merecem atenção especial, pois representam mistura complexa de contaminantes no ambiente, podendo causar efeitos deletérios a biota. Esses compostos possuem alta produção, utilização, descarte incorreto, chegando a rede coletora de esgoto através principalmente, da excreção humana e de residuos da indústria farmaceutica e agropecuária. Em águas superficiais, contribuem na alteração do padrão de qualidade das águas e redução da biodiversidade de organismos aquáticos, afetando tanto os ecossistemas quanto a saúde humana. As técnicas convencionais de tratamentos de efluentes são insuficientes na remoção desses compostos e seus metabólitos, sendo assim, buscam-se técnicas avançadas capazes de reduzir esses resíduos nas águas. O processo de irradiação por feixe de elétrons vem mostrando resultados satisfatórios na degradação dos compostos farmacêuticos, podendo ser utilizado como alternativa ou complemento aos processos de tratamento de efluentes. O objetivo deste trabalho foi a avaliação ecotoxicológica de quatro compostos farmaceuticos, isolados e em diferentes misturas (binárias, ternárias e quaternárias), bem como a aplicação da irradiação por feixe de elétrons, como proposta de tratamento para a redução dos efeitos tóxicos. Foram realizados ensaios com o antidepressivo Fluoxetina, o β-bloqueador Propranolol, o antibiótico Sulfadiazina e o estimulante Cafeína, individuais e combinados, antes e após o processo de irradiação. Os organismos-teste utilizados foram o microcrustáceo Daphnia similis e a bactéria Vibrio fischeri. A avaliação de risco através da concentração prevista sem efeito (PNEC), e a interação das misturas binárias (MixTox) também foram abordados no presente estudo. Os resultados dos ensaios de toxicidade para efeitos agudos dos fármacos individuais indicaram possível risco de sua presença para a biota aquática, quanto ao Propranolol e a Cafeína. Nas análises das interações toxicológicas das misturas binárias, foi identificado sinergismo para a mistura de Fluoxetina com Propranolol, e antagonismo para a mistura de Fluoxetina com Sulfadiazina e com a Cafeína. A irradiação por feixe de elétrons foi eficaz na redução da toxicidade dos compostos combinados. Na mistura binária de Fluoxetina com o Propranolol, a eficiência de remoção da toxicidade foi de 80% para D. similis e 30% para V. fischeri, nas doses de 2,5 e 5,0 kGy. A mistura de Fluoxetina com Sulfadiazina apresentou valores entre 20-30% de redução da toxicidade para ambos os organismos e doses aplicadas. Os resultados da mistura de Fluoxetina com Cafeína apresentaram eficiência de remoção da toxicidade de 45% para D.similis e 30% para V.fischeri, nas doses aplicadas. Nas misturas ternárias, a eficiência de remoção de toxicidade foi de 40% e 55% para V. fischeri, e de 25% e 35% para D. similis, respectivamente nas doses de 2,5 e 5,0 kGy. Na mistura quaternária a redução da toxicidade chegou a 80% para V. fischeri versus 60% para D. similis, na dose de 5,0 kGy; e em 40%, para ambos os organismos, na dose de 2,5 kGy. Houve o decaimento da absorbância em todos os comprimentos de onda característicos das amostras, indicando que o processo de irradiação foi eficiente na degradação dos compostos, porém baixa eficiência de remoção de carbono orgânico total, indicando que não houve mineralização significativa das amostras irradiadas.
Electron beam irradiation applied for the detoxification and degradation of single ciprofloxacin aqueous solution and multiclass pharmaceutical quaternary mixture
2023 - TOMINAGA, FLAVIO K.; BOIANI, NATHALIA F.; SILVA, THALITA T.; SANTOS, JONAS G. dos; LEBRE, DANIEL T.; LEO, PATRICIA; BORRELY, SUELI I.
The application of electron beam irradiation for detoxification and degradation of single antibiotic ciprofloxacin (CPF) and in a mixture with multiclass pharmaceuticals in aqueous solutions was carried out. Ecotoxicity assays indicated that the green algae were most sensitive to antibiotic and also that the presence of several pharmaceutical increased the toxicity. After the irradiation treatment, degradation results of single antibiotic indicated reduction of 95.86 % at 1.0 kGy. Total organic carbon decreased up to 38 % at 5.0 kGy. At lower doses (1.0 kGy), no effect in toxicity was evidenced, however, increase in toxicity for Vibrio fischeri was observed after 2.5 kGy. For Daphnia similis exposure, an increase in toxicity was noted for all applied doses. In contrast, for the green algae R. subcapitata toxicity reduction varied from 62.3 to 81.9 % at the evaluated doses. Toxicity assays to microbes E. coli and S. aureus reduced antibacterial activity of CPF after irradiation treatment. Regarding the irradiated quaternary mixture at 2.5 kGy, reduction up to 96 % was achieved for the ciprofloxacin, metformin and acetylsalicylic acid, and 81 % removal was achieved for fluoxetine. Acute assays with V. fischeri indicated no increase in toxicity, while some increase was noted for D. similis (acute effects). Nevertheless, chronic assays data indicated low toxicity reduction (14 %) with D. similis, and complete detoxification was shown for the green algae after the irradiation. In addition, decrease in antimicrobial activity was noted after the treatment. Furthermore, the in-silico model was not enough accurate for the prediction of CIP toxicity. These findings showed that electron beam irradiation can be applied for reducing the impacts of antibiotics in aquatic ecosystem. Measuring toxicity on living-organism from different trophic levels are useful tools to evaluate the interaction of mixtures and also to assess toxicity of the generated byproducts.
Toxicity removal of pharmaceuticals mixtures through electron beam irradiation
2022 - BOIANI, N.F.; TOMINAGA, F.K.; BORRELY, S.I.
Contamination of the aquatic environment by pharmaceuticals is becoming a global phenomenon of growing concern. Pharmaceuticals are partially metabolized, resulting in the excretion and release of residual into sewage, unaltered or metabolites. The wastewater treatment plants are not designed to eliminate these compounds, leading the residues into the aquatic environment. Besides, pharmaceuticals are not detected individually but as a complex mixture. Advanced oxidative processes have been applied as an alternative or complement to conventional sewage treatment processes, aiming the degradation and removal of toxic pollutants. The objective of this study was to evaluate the toxicity removal of mixtures of pharmaceuticals subjected to electron beam treatment. The aqueous solutions of each pharmaceutical were diluted in ultra-pure water and prepared in three pharmaceuticals combinations: Propranolol + Fluoxetine + Sulfadiazine; Propranolol + Fluoxetine + Diclofenac; Acetylsalicylic acid + Fluoxetine + Metformin). Electron Beam Accelerator was applied for the irradiations and the absorbed doses were 2.5-5.0 kGy. Acute toxicity tests with Daphnia similis were performed to evaluate the toxicity, before and after irradiation.. The data analyzed showed toxicity removal efficiency around 80% for the mixture of Propranolol, Fluoxetine and Diclofenac; 75% for the mixture of Propranolol, Fluoxetine and Sulfadiazine; and 30% for the mixture of Acetylsalicylic acid, Fluoxetine and Metformin. According to the literature, this is a viable technology for the removal of toxicity from pharmaceuticals, and the results demonstrated the potential of electron beam irradiation in reducing the toxicity of pharmaceutical from different classes.
Toxicity removal of pharmaceuticals mixtures through electron beam irradiation
2021 - BOIANI, N.F.; TOMINAGA, F.K.; BORRELY, S.I.
Is ionizing radiation effective in removing pharmaceuticals from wastewater?
2021 - TOMINAGA, FLAVIO K.; SILVA, THALITA T.; BOIANI, NATHALIA F.; JESUS, JULIANA M.S. de; TEIXEIRA, ANTONIO C.S.C.; BORRELY, SUELI I.
Wastewater and effluent discharges are the main causes of receiving water body pollution and important challenges in water quality management. Among the emerging contaminants, pharmaceuticals have increasingly drawn attention due to their incomplete removal during conventional biological treatment, inducing potential and actual risks to living organisms following residue discharges in river effluent. Electron beam irradiation (EBI) is a clean process technology for organic compound degradation and mineralization, as well as persistent pollutant detoxification. This study aimed to evaluate EBI effects on the degradation and toxicity removal of anti-inflammatory aspirin (ASA) in a single solution and in a fluoxetine (FLX) mixture. Results indicate that 98% of the single aspirin was degraded at 5.0 kGy. Aspirin toxicity to Daphnia similis, however, increased with increasing absorbed dose (1.0 to 5.0 kGy), possibly as a result of the presence of H2O2 and other byproducts formed during the oxidation process. Regarding the irradiated mixture, complete degradation was achieved for both pharmaceuticals. Toxicity removals for the mixture were of 56.2 ± 0.9% and 58.8 ± 5.4% for 1.0 and 2.5 kGy, respectively. These findings demonstrate that EBI can be an interesting alternative process to be applied as a pre-treatment followed by biological treatment.
Electron beam irradiation of pharmaceuticals aiming at toxicity reduction
2019 - BOIANI, N.F.; SILVA, V.H.O.; GARCIA, V.S.G.; DEL SOLE, S.V.; BORRELY, S.I.
Significant evidence is available in the literature justifying the search for treatment technologies or process combinations to improve the decomposition of dozens of pharmaceuticals in wastewater. Conventional processing techniques are insufficient in removal of the pharmaceuticals, for having resistant waste and low biodegradability. Electron beam irradiation (EBI) may play an important role in this context, and relatively low doses have been reported for such purposes. The objective of this study was to apply the process of irradiation with electron beam in order to reduce the toxic effects of fluoxetine, propranolol, and a binary mixture of these pharmaceuticals in aqueous solution. Ecotoxicological tests conducted in two model organisms, Daphnia similis microcrustacean, and Vibrio fischeri bacterium. It was observed that D. similis was more sensitive to the pharmaceuticals and binary mixture, when compared to V. fischeri. When EBI was applied, all doses showed significant reduction of toxicity for D. similis, and the opposite for V. fischeri, when only 5.0 kGy showed a significant reduced of toxicity for the pharmaceuticals and binary mixture. 5.0 kGy was the best removal efficiency for toxicity, approximately 80% for D. similis and 20% for V. fischeri.
Toxicity of textile effluents treated by electron beam technology
2019 - GARCIA, VANESSA S.G.; BOIANI, NATHALIA F.; ROSA, JORGE M; BORRELY, SUELI I.
The textile industry uses expressive amount of water during the production and generate effluents that contain residuals of dyes, surfactants, peroxides, acids and salts, and toxicity. In addition, the textile effluents are commonly colored, because the dyes used in fibers dyeing usually have low fixation and high solubility. Many of the mentioned products are not easily removed, requiring additional treatment steps. Advanced Oxidative Processes, such as electron beam irradiantion (EBI), can be a good alternative to reduction of organic pollutants from effluents. Therefore, studies on these contaminants in aquatic environment are important for assessing their impacts on ecosystems and water quality. The objective of this study was to evaluate the toxicity of textile effluents treated with EBI. The doses of 2.5 kGy and 5.0 kGy were used. The toxicity assays were performed with Daphnia similis organisms, exposed to samples during 48 hours, and the results expressed by EC50 (median effective concentration). For the textile effluent, EC 50% values ranged from: 2.95 ±0.13 (raw effluent) until 20.90 ±1.48 (irradiated effluent, at 5kGy). The EBI treatment was effective for toxicity reduction, with efficiency higher than 60% (2.5 kGy) and 80% (5.0 kGy). The study of organic and inorganic contaminants, presents in these effluents, demonstred EC 50 values below 5%. These results demonstrate high toxicity of contaminants from textile effluents for aquatic organisms (D. similis, cladocera). Similar data was observed for the raw effluent. These values are relevant for thinking radiation as a possible technology for such a type of effluent.
Electron beam irradiation of combined pharmaceuticals
2019 - BOIANI, NATHALIA F.; VILLARDI, BRUNO D.Q.; GARCIA, VANESSA S.G.; BORRELY, SUELI I.
There are serious evidences that justify the search for treatment technologies or processes combination for the improvement of decomposition for dozens of pharmaceuticals in wastewaters. Electron beam irradiation may play an important role in this scenario and relatively low doses have been reported for such purposes. The aim of the present study was to evaluate the toxic response of the crustacean Daphnia similis exposed to individual and combined pharmaceuticals. Several experimental trials of an acute immobilization test were performed with a mixture of pharmaceuticals composed of fluoxetine hydrochloride (Prozac®), and propranolol. Single pharmaceuticals were first tested separately. Toxicity of binary mixture was then assessed using five concentrations and 5 percentages of each substance in the mixture (0, 25, 50, 75, and 100%). Acute EC50% values ranged from 5.0 to 7.4 for fluoxetine and from 11.3 to 13.7 for propranolol. In mixture, values ranged from 6.4 to 9.8. Fluoxetine was more toxic for D.similis than propranolol. The different pharmaceuticals concentrations employed in a mixture showed no difference in toxicity values. When electron beam irradiation was applied, approximately 80% of acute effects were reduced at 5 kGy, and the mixture containing a higher percentage of fluoxetine, also showed a greater reduction of toxicity.
Electron beam irradiation of textile effluents and non-ionic ethoxylated surfactant for toxicity and color removal
2019 - BORRELY, S.I.; SILVA, L.G.A.; DEL SOLE, S.V.; GARCIA, V.S.G.; BOIANI, N.F.; ROSA, J.M.
Textile industry has an expressive scenario in the world economy and Brazil is the 5th in the textile production. By 2015, Brazilian textile production represented US $ 39.3 billion, accounting for more than 1.8 million tons of fabric. The effluents from textile industry are highlighted by quantity of wastewater discharged and variety of substances (dyes, bleaching agents, surfactants, salts, acids, among others). Such compounds often prove to be toxic to aquatic biota. This present study aims to assess toxicity of whole effluents, before and after irradiation (by electron beam accelerator, EBI). In addition, the reduction of the effluent color after irradiation is also very important. Daphnia similis and Vibrio fischeri were the biological systems applied for toxicity evaluations. Previous results demonstrated the surfactant as the main toxic compound, in the untreated and irradiated forms, EC 50 = 0.44 ppm ± 0.02 (untreated); EC 50 = 0.46 % ± 0.07 (irradiated). The irradiation was effective for reducing color of the effluent, starting from 0.5 kGy. EB irradiation may be proposed as an alternative treatment for the final effluent from textile processing, mainly for reuse purposes.