Assessment of novel Advanced Oxidation Processes for the Simultaneous Disinfection and Decontamination of Water

[ES] El mundo se enfrenta a una profunda crisis asociada al agua y la reutilización de aguas residuales urbanas (UWW), especialmente en agricultura, se presenta como una posible solución para abordar este problema. No obstante, la reutilización se debe promover dentro de unos límites mínimos de calidad del agua, los cuales pueden alcanzarse mediante la implementación de eficientes tratamientos terciaros en las actuales plantas de tratamiento de aguas residuales urbanas. En las últimas décadas, los Procesos de Oxidación Avanzada (POA), basados en la generación de especies reactivas del oxígeno altamente oxidantes y no selectivas, se han planteado como alternativa a los tratamientos convencionales para desinfección y descontaminación de agua residual. El objetivo general de este estudio es, por tanto, la evaluación de nuevos POA para desinfección y descontaminación simultánea de agua, investigando: (i) fotocatálisis heterogénea solar con ZnO modificado (Ce, Yb y Fe) y TiO2-P25 de referencia, (ii) peroximonosulfato (PMS) bajo radiación solar natural (PMS/Solar), (iii) POA basados en radical sulfato utilizando PMS y radiación UV-C (PMS/UV-C) y (iv) combinación de ZnO modificado con PMS como estrategia de tratamiento. Los objetivos biológicos y químicos analizados en este estudio fueron: tres patógenos de impacto en salud humana (dos bacterias gram-negativas Escherichia coli, Pseudomonas spp y una gram-positiva Enterococcus spp) y tres Contaminantes de Preocupación Emergente (CE) (Diclofenaco-DCF, Sulfametoxazol-SMX y Trimetoprim-TMP). La fotoactividad de ZnO modificado con Ce, Yb o Fe se evaluó a escala de laboratorio (200 mL), obteniendo buenas cinéticas de inactivación bacteriana y degradación de CE. El ZnO-Ce mostró el mejor rendimiento, no obstante, se descartó el escalado de este proceso tanto su aplicación directa, considerando su similar eficiencia en comparación con TiO2-P25 y por el alto coste del tratamiento, como en combinación con PMS, por la la liberación de Zn2+ al agua tratada. El uso directo de PMS como agente oxidante para el tratamiento de agua y UWW se ha demostrado en este estudio, aumentado su eficiencia al ser el sistema irradiado tanto con lámparas UV-C como con luz solar natural. Se han postulado diferentes mecanismos de inactivación y degradación de CE para cada tipo de irradiación: activación de PMS para generar radicales (con fotones UV-C) y la no activación o mecanismo de oxidación directo (con luz solar natural). La capacidad de los procesos PMS/Solar y PMS/UV-C se evaluó en UWW a escala de planta piloto en un Colector Parabólico Compuesto (10 L) y en una planta piloto de UV-C (80 L), respectivamente. El mejor rendimiento de tratamiento se alcanzó con una concentración de PMS de 1 mM en ambos casos, logrando una inactivación exitosa de todos los objetivos microbianos (incluyendo bacterias resistentes a antibióticos), sin observar recrecimiento bacteriano tras 48 h y eliminando de manera eficiente los CE. Por otro lado, la eliminación eficiente de genes de resistentes a antibióticos y productos de transformación se obtuvo con PMS/UV-C, mientras que éstos parámetros siguen siendo un reto a abordar en el caso del proceso PMS/Solar. En ningún caso se observó toxicidad del agua tratada para Aliivibrio fischeri, excluyendo un efecto nocivo para el medio ambiente receptor del efluente, y solo un leve efecto fitotóxico en el crecimiento de dos de las tres semillas analizadas (L. sativum y S. alba), indicando la idoneidad del efluente para su reutilización en riego. Finalmente, el análisis de costes demostró que este factor clave podría ser una barrera importante para la implementación del proceso PMS/Solar en plantas centralizadas de tratamiento de UWW. No obstante, su consideración como sistemas descentralizados asociados a pequeños volúmenes de agua en zonas con alta incidencia de radiación solar, ahorrando costes energéticos mediante el aprovechamiento de la luz solar, podría ser una opción real y asequible.[CA] El món s'enfronta a una profunda crisi associada a l'aigua i la reutilització d'aigües residuals urbanes (UWW), especialment en agricultura, es presenta com una possible solució per a abordar aquest problema. No obstant això, la reutilització s'ha de promoure dins d'uns límits mínims de qualitat de l'aigua, els quals poden aconseguir-se mitjançant la implementació d'eficients tractaments terciaris en les actuals plantes de tractament d'aigües residuals urbanes. En les últimes dècades, els Processos Avançats d'Oxidació (PAO), basats en la generació d'espècies reactives d'oxigen altament oxidants i no selectives, s'han plantejat com a alternativa als tractaments convencionals per a desinfecció i descontaminació d'aigua residual. L'objectiu general d'aquest estudi és, per tant, l'avaluació de nous POA per a desinfecció i descontaminació simultània d'aigua, investigant: (i) fotocatàlisi heterogènia solar amb ZnO modificat (Ce, Yb i Fe) i TiO2-P25 de referència, (ii) peroximonosulfat (PMS) baix radiació solar natural (PMS/Solar), (iii) POA basats en radical sulfat utilitzant PMS i radiació UV-C (PMS/UV-C) i (iv) combinació de ZnO modificat amb PMS com a estratègia de tractament. Els objectius biològics i químics analitzats en aquest estudi van ser: tres patògens d'impacte en salut humana (dos bacteris gram-negatius Escherichia coli, Pseudomonas spp i un gram-positiu Enterococcus spp) i tres Contaminants de Preocupació Emergent (CE) (Diclofenac-DCF, Sulfametoxazol-SMX i Trimetoprim-TMP). La fotoactivitat de ZnO modificat amb Ce, Yb o Fe es va avaluar a escala de laboratori (200 mL), obtenint bones cinètiques d'inactivació bacteriana i degradació de CE. El ZnO-Ce va mostrar el millor rendiment, no obstant això, es va descartar l'escalat d'aquest procés tant mitançant la seua aplicació directa o com en combinació amb PMS, considerant la seua similar eficiència en comparació amb TiO2-P25, l'alt cost del tractament i l'alliberament de Zn2+ a l'aigua tractada. L'ús directe de PMS com a agent oxidant per al tractament d'aigua i UWW s'ha demostrat en aquest estudi, augmentat la seua eficiència quan el sistema és irradiat tant amb llums UV-C com amb llum solar natural. S'han postulat diferents mecanismes d'inactivació i degradació de CE per a cada tipus d'irradiació: activació de PMS per a generar radicals (amb fotons UV-C) i la no activació o mecanisme d'oxidació directe (amb llum solar natural). La capacitat dels processos PMS/Solar i PMS/UV-C es va avaluar en UWW a escala de planta pilot en un Col·lector Parabòlic Compost (10 L) i en una planta pilot d'UV-C (80 L), respectivament. El millor rendiment de tractament es va aconseguir amb una concentració de PMS d'1 mm en tots dos casos, aconseguint una inactivació reeixida de tots els objectius microbians (incloent bacteris resistents a antibiòtics), sense observar recreixement bacterià després de 48 h i eliminant de manera eficient els CE. D'altra banda, l'eliminació eficient de gens de resistents a antibiòtics i productes de transformació es va obtindre amb PMS/UV-C, mentre que aquests paràmetres continuen sent un repte a abordar en el cas del procés PMS/Solar. En cap cas es va observar toxicitat a l'aigua tractada per a Aliivibrio fischeri, excloent un efecte nociu per al medi ambient receptor de l'efluent, i només un lleu efecte fitotòxic en el creixement de dos de les tres llavors analitzades (L. sativum i S. alba), indicant la idoneïtat de l'efluent per a la seua reutilització en reg. Finalment, l'anàlisi de costos va demostrar que aquest factor clau podria ser una barrera important per a la implementació del procés PMS/Solar en plantes centralitzades de tractament de UWW. No obstant això, la seua consideració com a sistemes descentralitzats associats a xicotets volums d'aigua en zones amb alta incidència de radiació solar, estalviant costos energètics mitjançant l'aprofitament de la llum solar, podria ser una opció real i assequible.[EN] It is well recognized that the world is facing a water crisis and the reuse of urban wastewater (UWW) in agriculture, has been gaining attention as a reliable solution to address this problem. It is mandatory to promote the safe water reuse and minimum water quality limits could be achieved by upgrading the Urban Wastewater Treatment Plants, through the addition of an efficient tertiary treatment. In the last decades, Advanced Oxidation Processes (AOPs), relying on the potential generation of highly oxidant, reactive and non-selective Reactive Oxygen Species (ROS), have been raised as alternative to conventional treatments for both water disinfection and decontamination. The general aim of this study is the assessment of novel AOPs for the simultaneous disinfection and decontamination of water, investigating (i) solar heterogeneous photocatalysis, involving modified ZnO with Ce, Yb and Fe and the benchmark TiO2-P25, (ii) peroxymonosulfate (PMS) under natural solar radiation (PMS/Solar), (iii) Sulfate radical-based AOPs (SR-AOPs) involving PMS and UV-C radiation (PMS/UV-C) and (iv) combination of the best-performing photocatalytic material with PMS (PMS/modified ZnO). The involved biological and chemical targets in this study were: three human health impact pathogens (two gram-negative bacteria Escherichia coli, Pseudomonas spp. and the gram-positive Enterococcus spp.) and three Contaminants of Emerging Concern (CECs, Diclofenac-DCF, Sulfamethoxazole-SMX and Trimethoprim-TMP). Photoactivity of modified ZnO with Ce, Yb or Fe was assessed in 200-mL vessel reactors, attaining good target's removal kinetic rates. Best performing material was ZnO-Ce, but its feasibility for a further up-scaling was discarded both as photocatalyst alone, considering the similar performances obtained, compared to TiO2-P25 and the high treatment cost, and in combination with PMS, due to the release of high amount of Zn2+. PMS alone has been proven to be an effective oxidant agent for water and UWW treatment, increasing its effectiveness when illuminated with photons from UV-C lamps and natural sunlight. Nevertheless, different inactivation and CECs degradation mechanisms have been postulated for each type of irradiation, and according to the activation of PMS (with UV-C photons) or non-activation (under natural sunlight). The capability of PMS/Solar and PMS/UV-C processes were evaluated in actual UWW at pilot plant scale in 10-L Compound Parabolic Collector and in 80L UV-C pilot plant, respectively. Optimal load of PMS was found to be 1 mM in both cases, achieving successful inactivation of natural occurring bacteria and their antibiotic resistant counterparts, without observing bacterial regrowth after 48h and efficiently eliminating CECs. Efficient removal of antibiotic resistant genes (ARGs) and transformation products (TPs) was obtained by PMS/UV-C, while their elimination is still a challenge to be addressed in PMS/Solar process. Reclaimed UWW obtained by both PMS/Solar and PMS/UV-C process showed no toxicity towards Aliivibrio fischeri, excluding a harmful effect towards the receiving aquatic environment after effluent discharge, and a very slightly phytotoxic effect for growth of two out of the three tested seeds (L. sativum and S. alba), indicating the suitability of this water for its subsequent reuse for agriculture. The analysis of the treatment cost revealed that this key factor could be an important barrier for implementation of PMS/Solar process in large centralized UWW treatment plants. Nevertheless, its consideration as decentralized systems associated to small volume of water in areas with a high solar radiation incidence, saving energy costs by using natural solar radiation, could be a real and affordable option.Berruti, I. (2022). Assessment of novel Advanced Oxidation Processes for the Simultaneous Disinfection and Decontamination of Water [Tesis doctoral]. Universitat Politècnica de València. https://doi.org/10.4995/Thesis/10251/183052TESI

Co-existence in the Phoebetria albatrosses at Marion Island

Bibliography: pages 154-162.The aims of the present study are threefold. Firstly, the coexistence of the two closely related, normally allopatric, albatross species is investigated in their zone of overlap where interspecific competition for food resources and nesting space is likely to be most acute. Secondly, the genetic isolation of the two species is investigated, as co-existence implies increased interspecific social interaction with associated increased possibilities of hybridization. Thirdly, the two species' possible evolutionary histories are examined in relation to their ecologies. Logistical constraints prevented study of fusca and palpebrata on the feeding grounds, i.e. at sea, and feeding could be studied only indirectly

Corporate Venture Capital : parent firm value relationship : firm structure and environment as contingencies

More and more firms are implementing a division of Corporate Venture Capital (CVC) as a strategy to differentiate their portfolio and create value. Through investments in entrepreneurial ventures, companies acquire innovations and new technologies to maintain and increase competitive advantages. Nevertheless, the relationship between CVC and investing (parent) firm remains an important research topic to dive into. Starting from the contingency theory, I propose that a rise in company value via CVC investing is contingent on attentional mechanisms that discipline the selection of fresh investment opportunities. Focusing on U.S. American parent companies of CVC divisions, this dissertation examines the impact of industry and firm-specific determinants on CVC investment activity in various industries, as well as related effects on firm value. An increase in firm value connected with CVC investing, I believe, accrue to firms that adopt specified operational structures and operate in specific environments, with business similarity with the entrepreneurial ventures and operating in the same metropolitan area. I show evidence that parent firm value increases among companies investing in CVC that are operational concentrate and operate in low munificence environments. I find support for my research model in a sample of 1.989 firm-year observations and 159 U.S. American companies between 2000 and 2020. This analysis aims to show that managers of companies which are active in the CVC market should take into considerations the above-mentioned effects when approaching an investment in venture capital, in order to maximize the firm’s gains in terms of innovations and strategy.Cada vez mais empresas estão a implementar uma divisão de Corporate Venture Capital (CVC) como uma estratégia para diferenciar a sua carteira e criar valor. No entanto, a relação entre a CVC e a empresa (mãe) investidora continua a ser um importante tópico de investigação a aprofundar. Partindo da teoria da contingência, proponho que um aumento do valor da empresa através do investimento da CVC está dependente de mecanismos de atenção que disciplinam a seleção de novas oportunidades de investimento. Centrando-se nas empresas-mãe americanas das divisões CVC, esta dissertação examina o impacto da indústria e dos determinantes específicos da empresa na actividade de investimento CVC em várias indústrias, bem como os efeitos relacionados no valor da empresa. Um aumento no valor da empresa ligado ao investimento da CVC, creio eu, resulta em empresas que adotam estruturas operacionais específicas e operam em ambientes específicos, com semelhança de negócios com os empreendimentos empresariais e que operam na mesma área metropolitana. Mostro provas de que o valor da empresa mãe aumenta entre as empresas que investem em CVC que são concentradas operacionais e operam em ambientes de baixa munificência. Encontro apoio para o meu modelo de investigação numa amostra de observações de 1.989 de anos de empresa e 159 empresas americanas entre 2000 e 2020. Esta análise visa mostrar que os gestores de empresas activas no mercado de CVC devem ter em consideração os efeitos acima mencionados ao abordar um investimento em capital de risco

Development and Applications of a Novel Intermittent Solids Feeder for Pyrolysis Reactors

This PhD research addresses the challenge of feeding biomass residues into fluidized bed reactors for pyrolysis, through the development of a novel intermittent solid slug feeder, both for laboratory-scale and large-scale reactors. The new feeder can successfully handle biomass residues that are either too cohesive or thermally sensitive for traditional feeders. To optimize the novel feeder performance, a model for the pulsating solids flow was developed from experimental data collected with ideal slugs, as well as real biomass flow. The model was validated using both a laboratory-scale (\u3c 10 kg/hr) and large-scale feeder (\u3e 250 kg/hr). Several important variables were identified. They include the material flow properties, the pulse gas pressure and volume, and the feeding tube length and material. The goals of this study were to (a) characterize the fundamental dynamic behavior of the biomass slugs in the feeder, (b) maximize the solid-to-gas feeding ratio, and thus minimize energy consumption and cost, (c) minimize the accumulation of “straggler” biomass material in the feeding tube between pulses, and thus prevent biomass heating in the feeding tube, which can induce plugging, and (d) develop and validate a predictive model for the slug velocity at any location in the feeding tube, which can be applied to feeder design for any biomass feedstock. An advantage of the new large-scale feeder technology is that it can handle larger biomass particles than traditional feeder technologies. An issue with large particles is that they require relatively long drying, which must be optimized. A model was therefore developed for drying, which takes shrinkage, and internal and external mass transfer limitations into account. The thesis is supplemented with additional work based on the application of the novel feeder for pyrolysis studies with various biomass residues. The feeder technology made it possible to perform the first ever pyrolysis studies, in industrially-relevant equipment, on pure meat and bone meal residue, and on unmodified and undiluted Kraft lignin. Appendices include a business case-study of the implementation of the technologies developed in this thesis on large-scale pyrolysis and an additional pyrolysis study on tucumã seeds, which utilized the novel feeder

Cold treatment breaks dormancy but jeopardizes flower quality in Camellia japonica L.

Camellia japonica L. is an evergreen shrub whose cultivars are of great ornamental value. In autumn, after flower bud differentiation, dormancy is initiated. As in many other spring flowering woody ornamentals, winter low temperatures promote dormancy release of both flower and vegetative buds. However, warm spells during late autumn and winter can lead to unfulfilled chilling requirements leading to erratic and delayed flowering. We hypothesized that storing plants at no light and low temperature could favor dormancy breaking and lead to early and synchronized flowering in response to forcing conditions in C. japonica ‘Nuccio’s Pearl’. Plants with fully developed floral primordia were stored at dark, 7∘C, and RH > 90% for up to 8 weeks. To monitor endodormancy release during the storage, we evaluated the content of abscisic acid (ABA) in flower buds and the expression profiles of five putative genes related to dormancy and cold acclimation metabolism in leaves and flower buds. In addition, the expression of four anthocyanin biosynthesis pathway genes was profiled in flower buds to assess the effect of the treatment on flower pigment biosynthesis. At 0, 4, 6, and 8 weeks of cold treatment, 10 plants were transferred to the greenhouse and forced to flower. Forced plant flower qualities and growth were observed. The ABA content and the expression profiles of two dormancy-related genes (CjARP and CjDEH) suggested that dormancy breaking occurred after 6–8 weeks of cold treatment. Overall, plants treated for 6–8 weeks showed earlier vegetative sprouting, enhanced, and homogeneous flowering with reduced forcing time. Prolonged cold treatments also reduced flower size and longevity, anthocyanin content, and pigment biosynthesis-related gene transcripts. In conclusion, the cold treatment had a promotive effect on dormancy breaking but caused severe drawbacks on flower quality