Importancia biológica de la microcistina en aguas de riego y alternativas en su detección y degradación / Biological importance of microcistin in irrigation and alternative waters in its detection and degradation

Introducción: Las cianobacterias son microrganismos fotosintéticos, con capacidad de sintetizar una gran diversidad de metabolitos secundarios de interés para la industria, pero también han llamado la atención en las últimas décadas las toxinas denominas cianotoxinas, metabolitos que causan distintas alternaciones fisiológicas hasta llegar ocasionar la muerte de diferentes especies. Metodología: La determinación del estado de arte para el tema de cianobacterias se basó en una búsqueda bibliográfica en la base de datos especializada como Elservier, Springer, Google académico y MDPI basadas en palabras clave en español e inglés "microcistinas", "degradación de MC" y "cuantificación y detección de MC". Resultados: En la presente revisión considera dos áreas de caracterización de la microcistinas (MCs) las propiedades fisicoquímicas y propiedades biológicas, para entender su comportamiento e importancia tóxica en los sembradíos agrícolas y en la salud humana. Además de comprender alternativas para su degradación, por métodos fisicoquímicos como fotocatálisis y la gradación biológica por bacterias. Finalmente se mencionará algunos métodos actuales y en desarrollo, para la detección y cuantificación de estas MCs en ambientes acuáticos. Conclusiones: Las MCs tienen el potencial contaminar fuentes de agua como ríos y lagunas, causando daños a la salud humana y a las plantas agrícolas, tienen la capacidad de tolerar distintos cambios drásticos en factores fisicoquímicos y biológicos. Entre las alternativas reportadas la degradación bacteriana promete ser la más confiable. Finalmente, entre los distintos métodos para la detección de MCs, entre los métodos más aplicados son los inmunoensayos, debido a su versatilidad y estabilidad del método.

Introduction: Cyanobacteria are photosynthetic microorganisms, with the capacity to synthesize a great diversity of secondary metabolites of interest to the industry, but toxins called cyanotoxins have also attracted attention in recent decades, metabolites that cause different physiological alterations until they cause the death of different species. Methodology: The determination of the state of the art for the subject of cyanobacteria was based on a bibliographic search in specialized databases such as Elservier, Springer, Google Scholar and MDPI based on keywords in Spanish and English "microcystins", "MC degradation " and "quantification and detection of MC". Results: In the present review, two areas of characterization of microcystins are considered: the physicochemical properties and biological properties of microcystins (MC), to understand their behavior and toxic importance in agricultural crops and in human health.In addition to understanding alternatives for their degradation, by physicochemical methods such as photocatalysis and biological grading by bacteria.Finally, some current and developing methods will be mentioned for the detection and quantification of these MCs in aquatic environments. Conclusions: MCs have the potential to contaminate water sources such as rivers and lagoon, causing damage to human health and agricultural plants, they have the ability to tolerate different drastic changes in physicochemical and biological factors. Among the reported alternatives, bacterial degradation promises to be the most reliable. Finally, among the different methods for the detection of MCs, among the most applied methods are immunoassays, due to their versatility and stability of the method.

Antimicrobial photocatalysis using bio-hydrothermally synthesized Zinc oxide nanoparticles in the management of periodontitis: a prospective split-mouth, double-blind, randomized, controlled clinical trial

Abstract The antimicrobial activity of metallic nanoparticles (NPs) has been confirmed to fight a broad spectrum of microorganisms, through antimicrobial effects that are amplified when these particles are irradiated with light of the proper wavelength. This is the first study to use phytoconjugated Zinc oxide (ZnO) NPs containing traces of active biomolecules derived from Emblica officinalis (E. officinalis) plant extract in antimicrobial photocatalysis (PCT) during non-surgical periodontal therapy. Objectives This study aimed to evaluate the effects of repeated PCT application in the treatment of periodontitis, using a gel containing bio-hydrothermally synthesized ZnO NPs and visible light as an adjunct to scaling and root planing (SRP). Methodology In total, 16 systemically healthy volunteers with stage 3 grade B generalized periodontitis were recruited for this prospective double blind, randomized placebo-controlled trial. After receiving SRP, the subjects received the following interventions in a split-mouth design at baseline, 1 week and 1 month: Group 1 - Placebo gel + Sham PCT; Group 2 - Nano ZnO gel + Sham PCT; Group 3 - Placebo gel + PCT; and Group 4 - Nano ZnO gel + PCT. The site-specific profile of Porphyromonas gingivalis in the subgingival plaque and clinical parameters (Plaque Index, Gingival Index, Gingival Bleeding Index, Probing pocket Depth and Clinical Attachment Level) were assessed at baseline, 1 month and 3 months. Results All interventions tested caused participants' clinical and microbiological parameters to generally improve after 3 months. Subjects who received the Nano ZnO gel + PCT combination showed a sustained and progressive improvement in their treatment outcomes, a result that presented statistically significant differences from the outcomes obtained through the remaining interventions, at all time points during the study period. Conclusions The repeated application of PCT using bio-hydrothermally synthesized ZnO NPs can effectively complement SRP in the non-surgical treatment of Periodontitis.

Effect of exogenous CdS nanoparticle on the growth of Escherichia coli / 生物工程学报

Semiconductor nanoparticles generate photoelectrons and photo-induced holes under light excitation, and thus may influence the growth of microbial cells. The highly oxidative holes may severely damage the cells, while the photoelectrons may promote microbial metabolism. In this study, we evaluated the effect of exogenous cadmium sulfide (CdS) nanoparticles on bacterial growth using OD600 and colony forming unit (CFU) as indicators. The oxidase activities, the concentration of pyruvate and malondialdehyde, and the expression of relevant genes assessed by real-time fluorescent quantitative PCR were analyzed to investigate the effect of excited CdS on cellular metabolism. The results showed that the OD600 and pyruvate accumulation of E. coli increased by 32.4% and 34.6%, respectively, under light conditions. Moreover, the relative expression level of the division protein gene ftsZ was increased more than 50%, and the tricarboxylic acid cycle pathway gene icdA and gltA increased by 86% and 103%, respectively. The results indicated that photoelectrons could be used by microorganisms, resulting in promoted growth and metabolism. This study gives a deep insight into the interaction between nanoparticles and bacteria.

Degradation of Caffeine by Heterogeneous Photocatalysis Using ZnO with Fe and Ag

Abstract The organic compound caffeine when detected in environmental matrices such as surface waters and groundwater is considered as an emerging contaminant, in which its effects are still unknown. Therefore, in the present research, zinc oxide-based catalysts impregnated with iron and silver were prepared for the reaction of caffeine degradation by heterogeneous photocatalysis. The wet impregnation method with excess solvent was applied to the preparation of the materials, later they were characterized by adsorption of N2, X-ray diffraction and photoacoustic spectroscopy. Then, the photodegradation, photolysis and adsorption tests were carried out, in which it was observed that only the presence of the radiation or photocatalysts could not sufficiently degrade the caffeine, however when combined radiation with all the catalysts studied here presented degradation above 70% at the end of 300 minutes of the reaction, and the best catalyst studied was that containing 8% Ag in non-calcined ZnO. Thus, these results point out that the methodology employed in this research, both for the preparation of the catalysts and in the process of the photocatalysis reaction, was efficient in the degradation of the emerging contaminant, caffeine, which could later be used for a mixture of other contaminants.

Photocatalytic Degradation of Textile dye Orange-122 Via Electrospray Mass Spectrometry

Abstract This work reports the study of the potential application of Zn/TiO2 catalysts, obtained by the sol-gel method, in processes of environmental decontamination through the reactions of photodegradation of textile dye, followed by electrospray mass spectrometry. The catalysts synthesis was performed according to a 2² factorial design with repetition at the central point. The characterization techniques used were: N2 adsorption measurements (BET method), scanning electron microscopy with energy dispersive X-ray (MEV/EDS), X-ray diffraction and point of zero charge (PZC). The photocatalytic tests were performed in batch in the presence of sunlight, and to evaluate the degradation kinetics study, a rapid direct injection electrospray mass spectrometry (DI-ESI-MS) method has been developed. By the photocatalytic tests, the calcination temperature of 400 °C has shown the best results of discoloration for the reactive Orange-122 dye (99.76%) in a reaction time of 2h. The discoloration kinetics were a pseudo-first order, and a statistical analysis was performed to investigate the effects of the variables and to optimize the conditions of discoloration to the dye. After the reactional time of 2 h, an ion of m/z 441.5 was detected by ESI-MS, indicating that the photocatalytic process was effective for the degradation of the dye to secondary compounds.

Evaluación de un reactor para la degradación fotocatalítica de glifosato empleando un catalizador de TiO2-Mn / Evaluation of a reactor for the photocatalytic degradation of glyphosate with a catalyst TiO2-Mn / Avaliação de reator para a degradação fotocatalítica do glifosato usando um catalisador de TiO2-Mn

Resumen En el presente trabajo se evaluó la degradación fotocatalítica del herbicida glifosato en solución acuosa con un catalizador comercial (TiO2 Degussa P25) y un catalizador sintetizado a partir de TiO2 dopado con manganeso (TiO2-Mn), soportados en anillos de borosilicato de diámetro interno y externo de 6,52 mm y 7,59 mm, respectivamente, y una longitud aproximada de 9,43 mm, mediante el uso de un reactor continuo de lecho empacado. El catalizador fue caracterizado por FTIR, SEM-EDS y AFM, con lo cual se determinaron algunas propiedades físicas y químicas del mismo. Las condiciones de operación del reactor fueron un caudal de alimentación de 4,25 mL min-1 de una solución de glifosato de pH natural de 4,45 y un tiempo de retención de 1 h y 25 min, en el cual se llevaron a cabo ensayos de fotocatálisis heterogénea, fotólisis y adsorción por un tiempo de 150 min. De lo anterior, se obtuvieron los porcentajes de remoción y el orden de la reacción fotocatalítica para el catalizador soportado en los anillos. A partir de los estudios de degradación realizados, con el TiO2-Mn soportado en los anillos, se logró un porcentaje máximo de degradación de 39.19%, mientras que, con el catalizador comercial TiO2 Degussa P25, se alcanzó un 28.6% de remoción. El modelo de reacción que sigue la degradación del glifosato es de difusión intrapartícula, debido a los procesos difusivos en los que la molécula de glifosato es adsorbida en los poros del catalizador para luego ser degradada.

Abstract In this work, the photocatalytic degradation of the herbicide glyphosate in aqueous solution was evaluated. Assays were performed on a commercial catalyst (TiO2 Degussa P25) and a catalyst synthesized from TiO2 doped with manganese (TiO2-Mn) supported on borosilicate rings, with an internal and external diameter of 6.52 mm and 7.59 mm respectively, and an approximate length of 9.43 mm, using a continuous packed bed reactor. The synthesized catalyst was characterized with techniques as FTIR, SEM-EDS, and AFM, which allowed to evaluating its chemical and physical properties. The reactor operating conditions were a feed flow rate of 4.25 mL min-1 of a pH 4.45 glyphosate solution and retention time of 1 h and 25 min. In such experiments, heterogeneous photocatalysis, photolysis, and adsorption test were carried out for 150 min, obtaining results of degradation percentages and the order of photocatalytic reaction for the catalyst supported in the rings and the powder in suspension. From the removal studies, a maximum degradation percentage of 39.19% was reached with TiO2-Mn supported in the rings. In contrast, the commercial catalyst TiO2 Degussa P25 had a 28.6% of removal. The glyphosate degradation follows an intraparticle diffusion model due to a diffusive process, where the glyphosate molecule is adsorbed in the catalyst pores and then degraded.

Resumo Neste trabalho, a degradação fotocatalítica de glifosato em solução aquosa foi avaliada com um catalisador comercial (TiO2 Degussa P25) e sintetizado a partir de TiO2 dopado com manganês (Mn-TiO2) com suporte em anéis de borosilicato de diâmetro interno e externo de catalisador 6,52 mm e 7,59 mm, respectivamente e um comprimento de aproximadamente 9,43 mm, usando um leito empacotado reator contínuo. O catalisador sintetizado foi caracterizado com FTIR, SEM-EDS and AFM, o que permitiu a sua morfologia e composição. As condições de operação do reactor foi alimentada à velocidade de 4,25 mL min-1 de uma solução de pH natural de 4,45 glifosato e um tempo de retenção de 1 hora e 25 minutos; em que foram realizados ensaios de fotocatálise heterogénea, fotólise, tempo de adsorção de 150 minutos, obtendo-se como percentagens resultados de remoção e com a reação fotocatalítica para o catalisador suportado em anéis. A partir dos estudos, foi obtido uma taxa máxima de degradação com TiO2-Mn suportado em anéis de 39,19% em comparação com o catalisador comercial de TiO2 Degussa P25 com os quais obtiveram porcentagens de degradação de 28,6%. A degradação do glifosato segue um modelo de difusão intrapartícula devido ao processo difusivo em que a molécula de glifosato é adsorvida no catalisador poros logo a ser degradada.

A novel textile wastewater treatment using ligninolytic co-culture and photocatalysis with TiO2 / Un novedoso tratamiento de aguas residuales de la industria textil usando co-cultivos ligninolíticos y fotocatálisis con TiO2 / Um novo tratamento para águas residuais têxtis usando co-cultura ligninolítica e fotocatálise com TiO2

Abstract Textile industries produce effluent wastewater that, if discharged, exerts a negative impact on the environment. Thus, it is necessary to design and implement novel wastewater treatment solutions. A sequential treatment consisting of ligninolytic co-culture with the fungi Pleurotus ostreatus and Phanerochaete crhysosporium (secondary treatment) coupled to TiO2 /UV photocatalysis (tertiary treatment) was evaluated in the laboratory in order to discolor, detoxify, and reuse textile effluent wastewater in subsequent textile dyeing cycles. After 48 h of secondary treatment, up to 80% of the color in the wastewater was removed and its chemical and biochemical oxygen demands (COD, and BOD5) were abated in 92% and 76%, respectively. Laccase and MnP activities were central to color removal and COD and BOD5 abatement, exhibiting activity values of 410 U L-1 and 1 428 U L-1, respectively. Subjecting wastewater samples to 12 h of tertiary treatment led to an 86% color removal and 73% and 86% COD and BOD5 abatement, respectively. The application of a sequential treatment for 18 h improved the effectiveness of the wastewater treatment, resulting in 89% of color removal, along with 81% and 89% COD and BOD5 abatement, respectively. With this sequential treatment a bacterial inactivation of 55% was observed. TiO2 films were reused continuously during two consecutive treatment cycles without thermic reactivation. Removal percentages greater than 50% were attained. Acute toxicity tests performed with untreated wastewater led to a lethality level of 100% at 50% in Hydra attenuata and to a growth inhibition of 54% at 50% in Lactuca sativa. Whereas sequentially treated wastewater excreted a 13% lethality at 6.25% and an inhibition of 12% at 75% for H. attenuata and L. sativa, respectively. Finally, sequentially treated wastewater was reused on dyeing experiments in which 0.86 mg g-1 adsorbed dye per g of fabric, that is equivalent to 80% of dye adsorption.

Resumen Las industrias textiles producen un efluente que, si es descargado, ejerce un impacto negativo en el ambiente. Así, es necesario diseñar e implementar soluciones novedosas para el tratamiento de estos desechos. Con el fin de decolorar, detoxificar y reutilizar aguas residuales producidas en la industria textil en ciclos de tinturado subsecuentes, se evaluó en laboratorio un tratamiento secuencial, consistente en un cultivo ligninolítico con los hongos Pleurotus ostreatus y Phanerochaete crhysosporium (tratamiento secundario) acoplado con fotocatálisis TiO2/UV (tratamiento terciario). Después de 48 horas de tratamiento secundario, se removió hasta un 80% del color del agua residual y las Demandas Química y Bioquímica de Oxígeno (DQO y DBO5) fueron reducidas en 92 y 76% respectivamente. Las actividades Lacasa y MnP (410 U L-1 y 1428 U L-1, respectivamente) fueron centrales en la remoción de color y en la reducción de DQO y DBO5. Someter muestras de agua residual a 12 horas de tratamiento terciario resultó en una remoción de 86% de color, 73% de DQO y 86% de DBO. La aplicación de un tratamiento secuencial por 18 h incrementó su efectividad, lo cual resultó en 89% de remoción de color, además de 81% y 89% de remoción de DQO y DBO5 respectivamente. Con este tratamiento secuencial se observó una inactivación bacteriana del 55%. Las películas de TiO2 se reutilizaron continuamente durante 2 ciclos de tratamiento consecutivos sin reactivación térmica. Se alcanzaron porcentajes de remoción mayores al 50%. Las pruebas de toxicidad aguda llevadas a cabo con agua residual cruda produjeron un nivel de letalidad del 100% a 50% en Hydra attenuata y una inhibición de crecimiento del 54% a 50% en Lactuca sativa. El agua residual tratada secuencialmente produjo una letalidad del 13% a 6.25% y una inhibición del 12% a 75% para H. attenuata y L. sativa, respectivamente. Finalmente, el agua residual tratada secuencialmente fue reutilizada en experimentos de tinturado en los que la cantidad de colorante absorbido fue de 0.86 mg g-1 por g de tela, lo cual es equivalente a 80% de adsorción.

Resumo A indústria têxtil produz águas residuais que causam um impacto negativo ao meio ambiente quando são descartadas. Portanto, é necessário projetar e implementar novas soluções para seu tratamento. Um tratamento sequencial que consiste na co-cultura ligninolítica com os fungos Pleurotus ostreatus e Phanerochaete crhysosporium (tratamento secundário) acoplada à fotocatálise com TiO2/UV foi avaliado no laboratório para descolorir, desintoxicar e reutilizar água residual têxtil em ciclos subsequentes de tintura. Após 48 h de tratamento secundário, aproximadamente 80% da cor foi removida da água residual e sua demanda química e bioquímica de oxigênio (COD, e BOD5) foram diminuídas em 92% e 76%, respectivamente. A atividade de Laccase e MnP foram centrais na remoção da cor e diminuição de COD e BOD5, mostrando valores de atividade de 410 U L-1 e 1428 U L-1, respectivamente. Submeter as amostras de água residual a 12 h de tratamento terciário levou a uma remoção de 86% da cor e uma diminuição de 73% e 86% de COD e BOD5 respectivamente. A aplicação do tratamento sequencial por 18 h melhorou a efetividade do tratamento de águas residuais, resultando em 89% de remoção de cor e uma diminuição de 81% e 89% de COD e BOD5, respectivamente. Com este tratamento sequencial, observamos uma inativação bacteriana de 55%. As películas de TiO2 foram reutilizadas continuamente durante dois tratamentos consecutivos sem reativação térmica. Atingimos porcentagens de remoção acima de 50%. Os testes de toxicidade aguda feitos em água residual sem tratar causaram níveis de letalidades de 100% a 50% em Hydra attenuata e uma inibição do crescimento de 54% a 50% em Lactuca sativa. Enquanto água residual tratada sequencialmente causou uma letalidade de 13% a 6.25% e uma inibição de 12% a 75% para H. attenuata e L. sativa, respectivamente. Finalmente, a água residual tratada sequencialmente foi reutilizada em experimentos de tintura nos quais absorveu 0.86 mg g-1 por g de tecido, o que é equivalente a uma absorção de 80%.

Comparação dos processos de síntese e do desempenho de fotocatalisadores para a degradação do corante rodamina B / A comparison of synthesis processes and the performance of photocatalysts for the degradation of rhodamine B dye

RESUMO Nanopartículas de óxidos de titânio (TiO2), zinco (ZnO) e ferro (Fe3O4) podem ser utilizadas na foto-oxidação de poluentes orgânicos, e em muitas outras aplicações. No entanto, entre os desafios para aplicação tecnológica dos desenvolvimentos científicos da nanotecnologia dois aspectos ainda são pouco explorados: a investigação sobre os métodos de preparação de nanomateriais compatíveis com o ambiente, e o estudo sobre a variabilidade das propriedades de nanomateriais. Diferentes métodos de síntese de partículas de TiO2, ZnO e Fe3O4 foram usados para obter dispersões coloidais com nano e micropartículas desses semicondutores. As partículas de TiO2, ZnO e Fe3O4 obtidas foram testadas como fotocatalisadores e aumentaram a taxa de fotodegradação do corante orgânico rodamina B (RHB) em até 20,5 vezes. Foram selecionadas as rotas de síntese que melhor atendem aos princípios da Química Verde para obtenção de partículas de ZnO e TiO2. Entretanto, para a aplicação comercial dessas partículas, ainda é preciso reduzir a variação em seus desempenhos fotocatalíticos.

ABSTRACT Titanium (TiO2), zinc (ZnO), and iron (Fe3O4) oxides nanoparticles can be used photo oxidation, of organic pollutants, as well as in many other ways. However, among the challenges for technological application (scale-up) of scientific developments that include nanotechnology, two aspects are still rarely explored: research on environmentally compatible preparation methods of the nanomaterials as well as the study of the variability of the properties of the nanomaterials. Different methods for the synthesis of TiO2, ZnO and Fe3O4 particles were used to obtain sols with these semiconductor nano- and microparticles. The TiO2, ZnO and Fe3O4 particles obtained were tested as photocatalysts, and they increased the photodegradation rate of the organic dye rhodamine B up to 20.5 times. The synthetic routes for obtaining ZnO and TiO2 particles that best met the Green Chemistry principles were selected. However, for commercial application of these particles, it is still necessary to reduce the variation in their photocatalytic performance.

Otimização multivariada do processo foto-Fenton solar na remoção da demanda química de oxigênio em lixiviados de aterros sanitários / Multivariate optimization of solar photo-Fenton process for chemical oxygen demand removal in landfill leachate treatment

RESUMO A presente pesquisa objetivou otimizar o processo foto-Fenton solar no tratamento de lixiviados de aterros sanitários. O Delineamento Composto Central Rotacional associado à Metodologia de Superfície de Resposta foi aplicado para investigar três variáveis operacionais: razão de reagentes [H2O2]/[FeSO4.7H2O], fator de H2O2 e pH inicial, a fim de maximizar a remoção de matéria orgânica, em termos da demanda química de oxigênio (DQO). De acordo com os resultados, obteve-se elevada redução da DQO em 3 horas de fotocatálise solar (70,97 a 84,74%). Com base na análise de variância (ANOVA), a variável reposta pode ser descrita por um modelo quadrático, com elevado coeficiente de explicação, R2=0,9894. A análise das superfícies de resposta indicou que as condições ótimas foram: faixa de pH inicial entre 2,5 e 3,5; com pico em 2,79; e razões de reagentes [H2O2]/[FeSO4.7H2O] a partir de 6 até o nível máximo estudado (7,36). Calculou-se a concentração de peróxido de hidrogênio com base no fator de H2O2, atingindo o ponto crítico em 143,77% da quantidade estequiométrica de H2O2 necessária para a oxidação completa da matéria orgânica, isto é, 11.751,05 mg H2O2.L-1 para estabilizar uma DQO de 3.845,55 mg O2.L-1.

ABSTRACT This research aimed to optimize the solar photo-Fenton process in landfill leachate treatment. Central Composite Rotatable Design associated with the Response Surface Methodology was applied to investigate three operational factors: reagents ratio [H2O2]/[FeSO4.7H2O], H2O2 factor and initial pH, in order to maximize the organic matter removal, in terms of chemical oxygen demand (COD). According to the results, high COD reduction was obtained in three hours of solar photocatalysis (70.97 to 84.74%). Based on the analysis of variance (ANOVA), the response variable can be described by a quadratic model, with a high coefficient of determination, R2=0.9894. The analysis of response surfaces indicated that the optimum conditions were: initial pH range between 2.5 and 3.5, with a peak at 2.79, and reagents ratio range from 6 to the maximum level studied (7.36). Hydrogen peroxide concentration was calculated from the H2O2 factor, reaching the critical point at 143.77% of the stoichiometric amount of H2O2 needed for the complete oxidation of organic matter, that is, 11,751.05 mg H2O2.L-1 to stabilize a COD of 3,845.55 mg O2.L-1.

Simultaneous Synthesis and Characterization of Biomass Multi-elements Self-doped Titanium Dioxide by Ultrasonic Irradiation / 分析化学

The biomass multi-elements self-doped TiO2was synthesized simultaneously by ultrasonic irradiation assisted sol-gel method, and characterized by field emission scanning electron microscopy (FESEM), X-ray diffraction(XRD), X-ray photoelectron spectroscopy (XPS), UV-Vis diffuse reflectance spectroscopy (UV-Vis-DRS), Fourier transform infrared (FT-IR) spectroscopy, and photoluminescence (PL). The characterization results showed that,multiple elements, C, N, P, Cl and K, were doped in the composite TiO2. Compared with pure TiO2,the band gap of the composite catalyst was narrowed by 0.21 eV, and possessed more surface hydroxyl radical and active sites, lower recombination rate of photo-generated carriers, higher crystallinity and higher specific surface area. The photocatalytic ability of the composite catalyst was studied,using methylene blue (MB) as target pollutant. The experimental results showed that, under visible light irradiation,the degradation efficiency of methylene blue was up to 98% after photocatalytic reaction for two hours by the composite catalyst.

Research progress in photocatalysis of titanium dioxide nanowire / 口腔疾病防治

@#Because nanoparticles have particular characteristics, such as small size and surface effects, nano-TiO2 is widely used in air purification, wastewater treatment and self-cleaning. In recent years, TiO2 photocatalysis has thoroughly explored as a new titanium implant surface treatment method. Photocatalytic performance is better for TiO2 nanowires than for nano-TiO2 particles. Hence, these nanowires have received widespread attention with regard for their more specific surface area and surface energy, improved charge carrier transport efficiency, and enhanced charge collection efficiency. Photon-generated carrier transport moves in a one dimensional straight path along a nanowire, and this could decrease photoelectron loss. In this paper, we summarized the principles underlying, factors that influence, and applications involving TiO2 nanowire photocatalysis. Additionally, we describe its method of preparation and toxicity.

Nanocristales para degradación de un colorante contaminante / Nanocrystals for the degradation of a pollutant dye / Nanocristais para a degradação de um corante poluente

La fotoestabilidad de nanocristales (NCs) del grupo E-VI, como CdSe se aprovecha en procesos de fotocatálisis. Sin embargo, el contenido de metales tóxicos limita su aplicación en el ambiente en la remediación de residuos de las industrias textiles, de pieles y de papel. Se comparó la acción catalítica de CdS y ZnS, estabilizadas con dodecil sulfato de sodio y ácido etilendiaminotetraacético, respectivamente, para el tratamiento fotocatalítico del colorante azul de metileno (AM) con radiación UV. Las dos clases de NCs presentaron bandas de absorción desplazadas hacia 500 nm y bandas de emisión fluorescente a 430-440 nm. Estas características ópticas se atribuyen al tamaño (20-50 y 100-150 nm), confirmado por microscopía electrónica. La degradación del AM por NCs alcanzó rendimientos del 92% y 77% para ZnS y CdS respectivamente, mediante la producción fotocatalítica de radicales hidroxilos capaces de participar en procesos redox. En conclusión, NCs se aprecian como catalizadores eficientes para la remediación de AM, un colorante aromático heterocíclico de amplio uso industrial.

The photo-stability of nanocrystals (NCs) in II-VI group such as CdSe is used for photo-catalytic processes. The presence of toxic metals limits their implementation in environmental applications such as synthetic dyes treatment, which are found in textile, leather, and paper industries. NCs ZnS and CdS, stabilized in the presence of ethylendiaminetetraacetic acid and sodium dodecyl sulfate, respectively, were compared in the photo-catalytic treatment of methylene blue (MB), under UV light. The two kinds of NCs showed absorption bands displaced towards 500 nm and fluorescent emission bands around 430 nm. These optical properties are attributed to nano size as observed by scanning electron microscopy (20-50 and 100-150 nm). MB degradation by NCs reached yields up to 92% and 77% for ZnS and CdS, respectively, due to the photo-catalytic production of hydroxyl radicals capable of participating in redox processes. In conclusion, NCs catalyzed the remediation of MB, a heterocyclic aromatic dye of broad industrial use.

A fotoestabilidade do nanomateriais (NCs) do grupo II-VI como CdSe é usada em processos de fotocatálise. Mas a presença de metais tóxicos limita sua implementação no ambiente para remediar os residuos das industrias têxteis, de couro e de papel. Foi comparada a ação catalítica de ZnS e CdS, estabilizados na presenca de dodecil sulfato de sódio e ácido etilenodiamino tetra-acético, respectivamente, para o tratamento fotocatalítico de azul de metileno (AM) com radiação UV. Os dois tipos de NCs mostraram bandas de absorção perto de 500 nm e bandas de emissao fluorescente a 430-440 nm Estas propriedades ópticas são atribuídas ao tamanho (20-50 y 100-150 nm) confirmado por microscopia electrónica A degradação do AM por NCs alcancou rendimentos de 92% e 77% para ZnS e CdS respectivamente, através da produção fotocatalítica de radicais hidroxilo capazes de participar em processos redox Em conclusão NCs são vistos como catalisadores eficientes para a remediação de AM, um corante de amplia utilização industrial.

Simultaneous decolorization and detoxification of black reactive 5 using TiO2 deposited over borosilicate glass / Decoloración simultánea y la desintoxicación de reactivo negro 5 con TiO2 depositadas sobre el vidrio de borosilicato por la técnica de sedimentación / Descoloração simultânea e a desintoxicação do preto reativo 5 com TiO2 depositadas em vidro de borosilicato pela técnica de sedimentação

Objective. Removal and detoxification of azo dye by photocatalysis with TiO2. Materials and methods. TiO2 films were prepared by sedimentation at pH 1.3, using as support a borosilicate glass, annealed for 1 hour at 450 °C. Physical characterization was performed by Scanning Electron Microscopy, X-ray diffraction and UV/VIS spectrometry. Dye Black Reactive 5 removal was carried-out in a quartz photo-reactor. Results. Optical characterization revealed the films displayed evident TiO2 spherical particles of various irregular sizes, porous, and without fractures. The average crystal size was 77.5 nm and 77.7 nm for 50 °C (dried temperature) and 450 °C (annealed temperature) respectively. The energy of the band gap (GAP) was 3.02 and 2.68 eV respectively. Maximum concentration of dye that negatively affected color removal was 80 mg/L (17%). At lower dye's concentrations (10, 50 and 70mg/L) decolorization was greater than 80%. TiO2 films were reused for five consecutive cycles of 6 hours at 10 mg/L (>80%), and three cycles of 10 hours at 70 mg/L (> 80%). Toxicity results demonstrate that Daphnia magna was more sensitive than Lactuca sativa. Conclusion. TiO2 films obtained by sedimentation demonstrated a high reactive black 5 decolorization and COD removal (86% and 100%), as well as toxicity reduction.

Objetivo. Decolorización y disminución de la toxicidad de un azo colorante usando fotocatálisis con TiO2. Materiales y métodos. Las películas de TiO2 fueron crecidas por sedimentación a pH 1,3 empleando vidrio de borosilicato como sustrato. La caracterización física se realizó por medio de microscopía electrónica de barrido, difracción de rayos X y espectrometría de absorción UV/vis. Los estudios de remoción del colorante Negro Reactivo 5, se realizaron en un fotoreactor de cuarzo. Resultados. De acuerdo con la caracterización óptica, las películas de TiO2 presentaron partículas esféricas, con diferentes tamaños, irregulares y sin fracturas. El tamaño del cristal fue 77,5 nm y 77,7 nm para 50 y 450° C y la energía de banda prohibida fue 3,02 y 2,68 eV, respectivamente. La concentración máxima del colorante que afectó negativamente la remoción de color fue 80 mg/L (17%). A concentraciones más bajas de NR5 (10, 50 y 70 mg/L) la decoloración fue superior al 80%. Las películas de TiO2 se reutilizaron por 5 ciclos de 6 horas a 10 mg/L y 3 ciclos de 10 h a 70 mg/L. Los estudios de toxicidad en Lactuca sativa y Daphnia magna demostraron que D. magna fue más sensible que L. sativa. Conclusión. Las películas de TiO2 crecidas por sedimentación decoloraron el colorante negro reactivo 5 en un 86% y removieron la demanda química de oxígeno en un y 100%, igualmente redujeron la toxicidad.

Objetivo. Descolorar e diminuir a toxicidade de um corante azo utilizando fotocatálise com TiO2. Materiais e métodos. Os filmes de TiO2 foram obtidos por sedimentação a pH 1,3 usando vidro de borosilicato como substrato. A caracterização física foi realizada por microscopia eletrônica de varredura, difração de raios X e espectrometria de absorção UV/vis. Os estudos de remoção de corante Preto Reativo 5, foram realizados num fotorreator de quartzo. Resultados. De acordo com a caracterização óptica, os filmes de TiO2 presentearão partículas esféricas com tamanhos diferentes, irregulares e sem fracturas. O tamanho do cristal foi de 77,5 nm e 77,7 nm para 50 e 450°C e a energia de banda proibida foi 3,02 e 2,68 eV, respectivamente. A concentração máxima do corante que afetou negativamente a remoção de cor foi de 80 mg/L (17%), em concentrações mais baixas (70, 50 e 10 mg/L) a descoloração foi superior a 80%. Os filmes TiO2 foram reutilizados em 5 ciclos de 6 horas a 10 mg/L e 3 ciclos de 10 horas a 70 mg/L. Os estudos de toxicidade com Lactuca sativa e Hydra attenuata demonstraram que H. attenuata foi mais sensível que L. sativa. Conclusão. Os filmes de TiO2 obtidos por sedimentação descoloram o corante Preto Reativo 5 e removeram a demanda química de oxigénio em 86% e 100%, respectivamente; do mesmo modo reduziram a toxicidade.

Photocatalytic inactivation of cyanobacteria with ZnO/γ-Al2O3 composite under solar light.

Cyanobacteria were inactivated by using zinc oxide (ZnO) coated on the surface of g-Al2O3 as a photocatalyst and combining with sunlight. In vitro experiments indicate that axenic cultures of planktonic cyanobacteria lost their photosynthetic activity after photocatalyzed with sunlight exposure exceeding 24 hr. As for Oscillatoria tenuisa, nearly 92% of the cells lost their photosynthetic activity and the cell morphology was severely damaged during 24 hr of the reaction. However, in the case of Microcystis aeruginosa, lower photocatalytic inactivity efficiency was observed, which was attributed to extracellular polymeric secretions (EPSs) surrounding the cells. With a high dosage ZnO catalyst, the dissolved organic carbon (DOC) concentration of the Oscillatoria tenuisa suspension was increased by up to about 190% during photocatalysis. The increased suspension of DOC was attributed to increase liberation of extracellular organic and cell-wall polysaccharides during photocatalysis.

Photocatalytic degradation of phenol in water using TiO2 and ZnO.

Photocatalytic degradation of chemical pollutants in water was investigated using semiconductor oxide catalysts, zinc oxide (ZnO) and titanium dioxide (TiO2 ) and phenol as the substrate. Influence of various parameters such as characteristics of the catalyst, irradiation time, substrate and catalyst concentrations, pH etc. has been studied and optimum conditions for the complete degradation of phenol in water have been identified. In terms of activity and durability, TiO2 is far superior to ZnO. Mixing ZnO with TiO2 does not affect its activity significantly. The process is especially relevant in view of its potential for the treatment of wastewater containing pollutants, using solar radiation as the energy source.

Evaluación de tres métodos para la inactivación de coliformes y Escherichia coli presentes en agua residual doméstica, empleada para riego / Evaluation of three methods for the inactivation of coliforms and Escherichia coli present in domestic wastewaters used in irrigation / Avaliação de três métodos para a inativação de coliformes totais e Escherichia coli presentes em águas residuais domésticas utilizadas para a irrigação

Objetivo. Evaluar tres tratamientos (lagunaje, fotocatálisis con TiO2 y desinfección química) para la inactivación de coliformes totales y Escherichia coli presentes en agua residual doméstica empleada para riego agrícola. Materiales y métodos. El agua residual fue caracterizada por medio de análisis físicos, químicos y microbiológicos. Posteriormente fue sometida a un tratamiento de lagunaje facultativo (TLF), pos tratamiento fotocatalítico (PTFTiO2/UV) y pos tratamiento químico (PTQ NaClO). Valorando la capacidad desinfectante de cada uno de ellos para inactivar coliformes totales y E. coli. A continuación se procesaron tres nuevos lotes de agua residual y se utilizaron para realizar pruebas de riego a escala de laboratorio por 30 días, empleando como modelo plantas de Lactuca sativa variedad Batavia y evaluando la concentración inicial y final de los dos grupos. Resultados. El PTFTiO2/UV fue significativamente superior que TLFLF y el PTQ NaClO (p<0,0001) obteniendo 100% de inactivación para coliformes y E. coli a los 30 minutos de irradiación a escala de reactor. Respecto a las pruebas de riego de L. sativa se demostró que al utilizar el agua tratada por PTFTiO2/UV no se presentó contaminación con E. coli y coliformes a los 30 días de proceso. Por el contrario en las plantas regadas con agua tratada por TLF y PTQ NaClO se observó un incremento en las dos poblaciones generando un problema de contaminación de las hortalizas al finalizar la prueba de laboratorio. Conclusión. La fotocatálisis heterogénea TiO2 fue un método eficaz para la reducción de coliformes y E.coli en aguas residuales domésticas.

Objective. To evaluate three treatments (facultative stabilization ponds, heterogeneous photocatalysis with TiO2 and chemical disinfection with sodium hypochlorite) for the inactivation of coliforms and Escherichia coli presen in domestic wastewaters used in agricultural irrigation. Materials and methods. Wastewater was characterized by physical, chemical and microbiological analyses and was then exposed to a facultative pond treatment (FPT), post-photocatalytic treatment (PTFTiO2/UV) and post-chemical treatment (PTQNaClO) to assess the disinfecting capacity of each method in the inactivation of total coliforms and E. coli. Three new samples of wastewater were processed and used in irrigation tests on a laboratory-scale basis for 30 days, using Lactuca sativa cultivar. Batavia as a model plant and evaluating the initial and final concentrations of the two groups. Results. PTFTiO2/UV was significantly higher than FPT and PTQNaClO (p<0.0001), obtaining 100% of inactivation of coliforms and E. coli after 30 minutes of irradiation at a reactor scale. Regarding the irrigation tests with L. sativa, we showed that using water treated by PTFTiO2/UV there is no contamination with E. coli and coliforms after 30 days. On the contrary, plants irrigated with water treated by FPT and PTQNaClO showed an increase in the two populations originating a contamination problem in the vegetable by the end of the laboratory experiments. Conclusion. The heterogeneous photocatalysis with TiO2 was an effective method in the reduction of coliforms and E. coli present in domestic wastewater.

Objetivo. Avaliar três tratamentos (lagoas, fotocatálise com TiO2 e desinfecção química) para inativação de coliformes totais e Escherichia coli presentes em águas residuais domésticas utilizadas na irrigação dos cultivos. Materiais e métodos. O efluente foi caracterizado por analises físicos, químicos e microbiológicos. Posteriormente foi submetido a tratamento de lagoas facultativas (TLF), pós-tratamento fotocatalítico (PTF TiO2/UV) e pós-tratamento químico (PTQ NaClO). Avaliando a capacidade desinfetante de cada um para inativar coliformes totais e E. coli. Posteriormente, foram processados três novos lotes de águas residuais para testar a irrigação em escala de laboratório por 30 dias, utilizando-se como modelo plantas de Lactuca sativa variedade Batavia e avaliando a concentração inicial e final dos dois grupos. Resultados. O PTFTiO2/UV foi significativamente maior a TLFLF e PTQ NaClO (p<0,0001) apresentando 100% de inativação para coliformes e E. coli em 30 minutos de irradiação a escala do reator. Quanto aos testes de irrigação de L. sativa foi demonstrado que, ao utilizar a água tratada com PTFTiO2/UV não se apresentou contaminação com E. coli e coliformes a 30 dias do tratamento. Em contrapartida, em plantas irrigadas com água tratada por TLF e PTQ NaClO observou-se um aumento nas duas populações gerando um problema de contaminação de hortaliças no final do teste de laboratório. Conclusão. A fotocatálise heterogênea TiO2 foi um método eficaz para reduzirem coliformes e E. coli em águas residuais domésticas.

Evaluación de l degradación y mineralización dl malatión usando fotocatálisiss mediante un colecto ssolar / Evalution of deggradation and mineralization of the mlathion using pphotocatalysis with a solar collector / Avaliação dadegrradação e mineralização da fotocatálise utilzando malationaa comum coletor solar

Se empleó un colector solar para evaluar la degradación del malatión en una solución acuosa de 15 µg/L del plaguicida, usando tres concentraciones diferentes de dióxido de titanio (100, 200 y 250 mg/L) y peróxido de hidrógeno (H2O2) al 30% como agente oxidante. La disminución de la concentración del malatión se determinó por cromatografía de gases con detector de microcaptura de electrones (CG-µECD), previa extracción de las muestras con discos C18, y la mineralización se determinó mediante análisis de carbono orgánico total (COT). El proceso de degradación se evaluó durante 16 horas, durante las cuales, se registró la energía solar incidente mediante un radiómetro (Kipp & Zonen, modelo CUV 3). En la fotolisis se alcanzó un porcentaje de degradación de 58,8% y en la fotocatálisis, con 250 mg/L de TiO2 y 10 mL/h de H2O2, se obtuvo 98,7% de degradación. El porcentaje de mineralización alcanzado durante la fotocatálisis fue de 73%.

A solar panel was used to evaluate malat-hion degradation. A solution of 15 µg/L of malathion, three different concentrations of titanium dioxide (100, 200 y 250 mg/L) and hydrogen peroxide (H2O2)to 30% like a oxidant agent. Malathion concentration was determined by gas chromatography with CG-µECD previous preparation of sample using octadecyl (C18) extraction disks. The mineralization was determined by analysis of total organic carbon (TOC). The degradation process was evaluated for 16 hours, period during which the incident solar irradiation was registered by a radiometer (Kipp & Zonen, model CUV 3). 58,8% of degradation in photolysis and 98,7% of degradation in photocatalysis with 250 mg/L TiO2 and 10 mL/h H2O2 were reached. The percentage of mineralization reached during photocatalysis was 73%.

Um painel solar foi usado para avaliar malation degradação. Uma solução de 15 mg/L de malation, três diferentes concentrações de dióxido de titânio (100, 200 y 250 mg/L) e peróxido de hidrogênio (H2O2) a 30% como um agente oxidante. Malathion concentração foi determinada por anterior preparação da amostra utilizando cromatografia gasosa com CG-DCE octadecílico (C18) extração discos. A mineralização foi determinada por análise de carbono orgânico total (COT). O processo de degradação foi avaliado durante 16 horas, período durante o qual a radiação solar incidente foi registrada por um radiômetro (Kipp & Zonen, modelo CUV 3). 58,8% dedegra-dação em fotólise e 98,7% de degradação em fotocatálise com 250 mg/L TiO2 e10 mL/h H2O2 foram atingidos. A percenta-gem de mineralização atingido durante photocatalysis foi de 73%.

Fotodegradación de las aguas residuales con pesticida Mertect en la industria bananera empleando Fotocatálisis con Dióxido de Titanio y Lámpara de Luz Ultravioleta / Degradation of waste waters from the banana industry by the use of photocatalysis with titanium dioxide and ultra violet light lamp

Introducción. Los pesticidas son compuestos químicos sintéticos que poseen la característica de ser persistentes, lo cual favorece la contaminación de las aguas, la incorporación a suelos, pastizales, vegetales y animales comestibles, los que al ser consumidos actúan como transportadores de los pesticidas facilitando su acumulación en los organismos vivos en todos los eslabones de la cadena trófica; es por esta razón que reviste importancia los procesos de degradación y descontaminación de este tipo de contaminantes. Objetivo. Evaluar la fotodegradación del pesticida Mertect empleando fotocatálisis con dióxido de titanio y lámpara de luz ultravioleta. Materiales y métodos. En la experimentación se utilizó una lámpara de luz ultravioleta, una cuba de vidrio para el almacenamiento de la solución del pesticida a degradar y una bomba que permitía la recirculación de la solución por el sistema de tratamiento; la degradación del pesticida se determinó mediante espectrofotometría ultravioleta/visible. Para el análisis de la información se empleo el diseño experimental factorial 2³, completamente balanceado. Resultados. El porcentaje de remoción más alto fue de 99,5%; este se obtuvo para dos condiciones experimentales: 50 mg/L de dióxido de titanio y 1 %v/v de peróxido de hidrógeno, y 100 mg/L de dióxido de titanio y 1 %v/v de peróxido de hidrógeno. Conclusión. Los procesos de oxidación avanzados son adecuados para la remoción y eliminación del pesticida Mertect en las aguas residuales de la industria bananera.

Introduction. Pesticides are synthetic chemical compounds with the characteristic of being persistent, thus helping to contaminate water and incorporating pollutants to the soils and to edible vegetables and animals that, when eaten, act as pesticide transporters, accumulating that pesticide in living organisms from all the links of the trophic chain. This is the reason for the great importance of the degradation and decontamination processes of this kind of pollutants. Objective. To evaluate the photodegradation of the Mertect pesticide by the use of photocatalysis with titanium dioxide and ultra violet light. Materials and methods. In the experiment, an ultra violet light lamp, a glass bucket to store the pesticide to be degraded and a bomb to recirculate the solution trough the treatment system were used. The degradation of the pesticide was determined by visible/ultraviolet spectrophotometry. For the information analysis the 2³ experimental factorial designs was used, under complete balance. Results. The highest removal percentage was 99.5%, obtained for two experimental conditions: 50 mg /L of titanium dioxide and 1% v/v of hydrogen peroxide, and 100mg/L of titanium dioxide and 1%v/ v of hydrogen peroxide. Conclusions. Advanced oxidation processes are adequate to remove and eliminate the Mertect pesticide in the waste waters from the banana industry.

Preparation of TiO2 Nano-materials and Photocatalytic Purification of Sewage / 环境与健康杂志

The recent research progress of photo-catalyzed degradation of organic pollutants by TiO2 is reviewed,the characteristics of hydrothermal method and the prepared processes of TiO2 were discussed,the photo-catalyzed mechanism under UV and visible light and the application of degradation of sewage using TiO2 nanomaterials from five aspects were described in this paper. The main problems existing in the studies of TiO2,the research directions,and the development prospects were also discussed.

Effect of Air Sterilization with Nanometer Photocatalysis Air Sterilizer in Hospital / 中华医院感染学杂志

OBJECTIVE To observe the sterilization effect of nanometer photocatalysis air sterilizer mounted in hospital.METHODS We carried out a dynamic survey on air average numbers of colony through field experiment and practical operation.RESULTS The field experiment displayed that the air bacterium dissolution rate was 55.64-75.94% and the bacterium content degraded as time extended,after nanometer photocatalysis air sterilizer been used 1-2 h;the result of practical operation in four seasons of the year revealed that the average bacterium colony numbers in each ward region was lower than before sterilizer mounted,the air bacterium dissolution rate was 73-82.3% in the third ward region and 44.5-76.3% in the fourth ward region.CONCLUSIONS It is effective to use the nanometer photocatalysis air sterilizer to sterilize the air in hospital under the condition of inspection.The airflow of the central air conditioning can practice the air sterilization function more validly.