Degradação de ácido salicílico, cetoprofeno, diclofenaco, paracetamol e cafeína, pelo processo foto-Fenton mediado por ferrioxalato, irradiado com LEDs-UV

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dc.contributorUniversidade de São Paulo
dc.contributor.author1
dc.date.issued2020-05-26
dc.description.abstract<span style=\"font-weight: 400;\">Neste trabalho, insvestigou-se a ocorr&ecirc;ncia dos f&aacute;rmacos &aacute;cido salic&iacute;lico, cetoprofeno, diclofenaco, paracetamol e cafe&iacute;na em amostras de &aacute;guas superficiais do ribeir&atilde;o Feij&atilde;o, do c&oacute;rrego do Espraiado, entrada da Esta&ccedil;&atilde;o de Tratamento de &Aacute;gua (ETA), e das &aacute;guas destinadas ao abastecimento p&uacute;blico (sa&iacute;da da ETA) do munic&iacute;pio de S&atilde;o Carlos/SP durante um ano.&nbsp; Os analitos foram extra&iacute;dos e pr&eacute;-concentrados, utilizando-se um sistema semiautom&aacute;tico de extra&ccedil;&atilde;o em fase s&oacute;lida (SPE) e, ent&atilde;o, analisados por cromatografia l&iacute;quida de alta efici&ecirc;ncia com detector de arranjo de diodos (HPLC/DAD).&nbsp; O m&eacute;todo anal&iacute;tico desenvolvido foi validado e mostrou-se linear na faixa de 200 a 360 ng L<span style=\"font-weight: 400;\">-1<span style=\"font-weight: 400;\"> para o paracetamol, 120 a 280 ng L<span style=\"font-weight: 400;\">-1<span style=\"font-weight: 400;\"> para a cafe&iacute;na, cetoprofeno e diclofenaco e de 160 a 320 ng L<span style=\"font-weight: 400;\">-1<span style=\"font-weight: 400;\"> para o &aacute;cido salic&iacute;lico, com coeficientes de correla&ccedil;&atilde;o maiores que 0,99.&nbsp; Os limites de detec&ccedil;&atilde;o e quantifica&ccedil;&atilde;o foram de 36 e 120 ng L<span style=\"font-weight: 400;\">-1<span style=\"font-weight: 400;\"> para o diclofenaco, cetoprofeno e cafe&iacute;na, de 60 e 200 ng L<span style=\"font-weight: 400;\">-1<span style=\"font-weight: 400;\"> para o paracetamol e de 48 e 160 ng L<span style=\"font-weight: 400;\">-1<span style=\"font-weight: 400;\"> para o &aacute;cido salic&iacute;lico, respectivamente.&nbsp; A precis&atilde;o intradia variou entre 0,85 e 5,03%, os valores de recupera&ccedil;&atilde;o variaram entre 50 e 78%, e a exatid&atilde;o entre 98,89 e 101,20%.&nbsp; N&atilde;o foi detectada nenhuma das subst&acirc;ncias investigadas nas amostras analisadas durante o per&iacute;odo dos testes.&nbsp; Tamb&eacute;m avaliou-se a degrada&ccedil;&atilde;o desses f&aacute;rmacos pelo processo foto-Fenton irradiado LEDs-UV, assistido pelo ferrioxalato.&nbsp; Tr&ecirc;s fatores (pot&ecirc;ncia dos LEDs, concentra&ccedil;&atilde;o de Fe<span style=\"font-weight: 400;\">3+<span style=\"font-weight: 400;\"> e de H<span style=\"font-weight: 400;\">2<span style=\"font-weight: 400;\">O<span style=\"font-weight: 400;\">2<span style=\"font-weight: 400;\">) foram estudados via planejamento experimental.&nbsp; Usou-se uma fun&ccedil;&atilde;o desejabilidade que levasse em conta a degrada&ccedil;&atilde;o conjunta dos cinco f&aacute;rmacos.&nbsp; Os n&iacute;veis otimizados de cada fator (Pot&ecirc;ncia dos LEDs = 1,768 W;&nbsp; <span style=\"font-weight: 400;\">C<span style=\"font-weight: 400;\">Fe<span style=\"font-weight: 400;\">3+<span style=\"font-weight: 400;\"> = 15,0 mg L<span style=\"font-weight: 400;\">&ndash;1<span style=\"font-weight: 400;\">;&nbsp; e <span style=\"font-weight: 400;\">C<span style=\"font-weight: 400;\">H<span style=\"font-weight: 400;\">2<span style=\"font-weight: 400;\">O<span style=\"font-weight: 400;\">2<span style=\"font-weight: 400;\"> = 47,6 mg L<span style=\"font-weight: 400;\">&ndash;1<span style=\"font-weight: 400;\">) foram determinados utilizando-se a metodologia de superf&iacute;cie de respostas (MSR).&nbsp; No ponto &oacute;timo, todas as concentra&ccedil;&otilde;es dos f&aacute;rmacos analisados ficaram abaixo dos respectivos limites de detec&ccedil;&atilde;o ap&oacute;s 25 min de rea&ccedil;&atilde;o, 30% de mineraliza&ccedil;&atilde;o foi obtida e 40% de DQO foi removida.&nbsp; Ainda no ponto &oacute;timo, avaliou-se a cin&eacute;tica da rea&ccedil;&atilde;o e verificou-se que os f&aacute;rmacos estudados apresentaram comportamentos cin&eacute;ticos semelhantes (pseudo-primeira ordem), com r&aacute;pida degrada&ccedil;&atilde;o (aproximadamente 80% nos 10 min iniciais) e constantes de taxa virtualmente id&ecirc;nticas na ordem de 10<span style=\"font-weight: 400;\">-1<span style=\"font-weight: 400;\"> min<span style=\"font-weight: 400;\">-1<span style=\"font-weight: 400;\">.<span style=\"font-weight: 400;\">&nbsp; <span style=\"font-weight: 400;\">Durante a rea&ccedil;&atilde;o o o n&uacute;mero m&eacute;dio de oxida&ccedil;&atilde;o do carbono variou de <span style=\"font-weight: 400;\">&minus;<span style=\"font-weight: 400;\">2,7 para <span style=\"font-weight: 400;\">&minus;<span style=\"font-weight: 400;\">1,9 (ap&oacute;s 25 min).&nbsp; Os testes de ecotoxicidade (<span style=\"font-weight: 400;\">Latuca sativa<span style=\"font-weight: 400;\">) indicaram que, apesar da forma&ccedil;&atilde;o de subprodutos, n&atilde;o houve aumento da fitotoxicidade. &nbsp;
dc.description.abstract<span style=\"font-weight: 400;\">The occurrence of salicylic acid, ketoprofen, diclofenac, paracetamol and caffeine was investigated in surface water samples from Feij&atilde;o and Espraiado streams, entrance of the Water Treatment Plant (WTP), and waters intended for public supply (exit of the WTP) from the city of S&atilde;o Carlos/SP.&nbsp; The analytes were extracted and preconcentrated using a solid phase extraction (SPE) semiautomatic system and then analyzed by high performance liquid chromatography with diode array detector (HPLC/DAD).&nbsp; The developed analytical method was validated and its linear range was from 200 to 360 ng L<span style=\"font-weight: 400;\">-1<span style=\"font-weight: 400;\"> for acetaminophen, 120 to 280 ng L<span style=\"font-weight: 400;\">-1<span style=\"font-weight: 400;\"> for caffeine, ketoprofen, and diclofenac and from 160 to 320 ng L<span style=\"font-weight: 400;\">-1<span style=\"font-weight: 400;\"> for salicylic acid, with correlation coefficients greater than 0.99. The detection and quantification limits were 36 and 120 ng L<span style=\"font-weight: 400;\">-1<span style=\"font-weight: 400;\"> for diclofenac, ketoprofen and caffeine, 60 and 200 ng L<span style=\"font-weight: 400;\">-1<span style=\"font-weight: 400;\"> for paracetamol and 48 and 160 ng L<span style=\"font-weight: 400;\">-1<span style=\"font-weight: 400;\"> for salicylic acid, respectively. The intraday precision ranged from 0.85 to 5.03%, recovery ranged from 50 to 78%, and accuracy from 98.89 to 101.20%.&nbsp; None of the investigated substances were detected in the samples analyzed during the testing period.&nbsp; The degradation of those drugs by the photo-Fenton process irradiated with LEDs-UV and assisted by ferrioxalate was also evaluated.&nbsp; Three factors (LEDs power, Fe<span style=\"font-weight: 400;\">3+<span style=\"font-weight: 400;\"> and H<span style=\"font-weight: 400;\">2<span style=\"font-weight: 400;\">O<span style=\"font-weight: 400;\">2<span style=\"font-weight: 400;\"> concentrations) were studied via experimental design.&nbsp; A desirability function, taking into consideration the joint degradation of the five drugs, was used.&nbsp; The optimized levels of ea? factor (LEDs power = 1.768 W, <span style=\"font-weight: 400;\">C<span style=\"font-weight: 400;\">Fe<span style=\"font-weight: 400;\">3+<span style=\"font-weight: 400;\"> = 15.0 mg L<span style=\"font-weight: 400;\">&ndash;1<span style=\"font-weight: 400;\">, and <span style=\"font-weight: 400;\">C<span style=\"font-weight: 400;\">H<span style=\"font-weight: 400;\">2<span style=\"font-weight: 400;\">O<span style=\"font-weight: 400;\">2<span style=\"font-weight: 400;\"> = 47,6 mg L<span style=\"font-weight: 400;\">&ndash;1<span style=\"font-weight: 400;\">) were determined using the response surface meotodology (RSM).&nbsp; Under the optimized conditions, the concentrations of all drugs were below their respective detection limits after 25 min of reaction, 30% mineralization was achieved, and 40% of the COD was removed.&nbsp; The reaction kinetics (optimized conditions) were assessed and it was verified that the studied drugs presented similar kinetic behavior (pseudo-first order), with fast degradation (approximately 80% in the first 10 min), and virtually identical rate constants around 10<span style=\"font-weight: 400;\">-1<span style=\"font-weight: 400;\"> min<span style=\"font-weight: 400;\">-1<span style=\"font-weight: 400;\">.&nbsp; During reaction, the medium oxidation number of carbon ranged from <span style=\"font-weight: 400;\">&minus;<span style=\"font-weight: 400;\">2.7 to <span style=\"font-weight: 400;\">&minus;<span style=\"font-weight: 400;\">1.9 (after 25 min). Ecotoxicity tests (<span style=\"font-weight: 400;\">Latuca sativa<span style=\"font-weight: 400;\">) indicated that, despite the formation of byproducts, there was no increase in phytotoxicity.
dc.formatapplication/pdf
dc.identifier.doi10.11606/T.75.2020.tde-19052020-142838
dc.identifier.urihttp://www.teses.usp.br/teses/disponiveis/75/75135/tde-19052020-142838/
dc.languagept
dc.rights.holder1
dc.subjectLED
dc.subjectfármaco
dc.subjectvalidação
dc.subjectferrioxalato
dc.subjectfoto-Fenton
dc.subjectmetododologia de superfícies de resposta
dc.subjectresponse surface methodology
dc.subjectphoto-Fenton
dc.subjectdrug
dc.subjectLED
dc.subjectferrioxalate
dc.subjectvalidation
dc.titleDegradação de ácido salicílico, cetoprofeno, diclofenaco, paracetamol e cafeína, pelo processo foto-Fenton mediado por ferrioxalato, irradiado com LEDs-UV
dc.title.alternativeDegradation of salicylic acid, ketoprofen, diclofenac, pracetamol and caffeine by the ferrioxalate-mediated photo-fenton process, irradiated with UV-LEDs
dc.typeTese de Doutorado
usp.advisorAzevedo, Eduardo Bessa
usp.date.defense2020-03-06
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