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Innovative Desinfektionsverfahren zur Brauchwassergewinnung in der dezentralen Abwasserbehandlung - Elektrolyse und UV/Elektrolyse-HybridtechnikHaaken, Daniela 10 August 2015 (has links) (PDF)
According to estimates of the United Nations Environment Programme (UNEP), more than 1.8 billion people will be living in countries or regions with absolute water scarcity by 2025. The pressure on water resources is increased not only in arid and semiarid regions, but also in fast growing megacities around the world as a result of, amongst other factors, the changing nutritional and consumer behavior (rising living standards). Over 90 % of the annual water consumption of the newly industrializing and developing countries in the arid and semiarid climate zone is used for agricultural irrigation to ensure the nutrition of the population. Thus, since the beginning of the 20th century, the planned/controlled reuse of wastewater has developed into a central task of the sustainable water resources management. Wastewater represents a valuable resource in view of its composition (e. g. nutrients P, N for soil fertilizing) and its reliable, weather-independent availability in every household. The establishment of a closed-loop water management can enhance the efficiency of water usage. Therefore, activities in research and development are currently focused on decentralized and semi-centralized concepts, since their structures offer better conditions for the establishment of closed-loop systems and innovations in wastewater technology can be implemented more easily.
In general, the hygienic quality requirements for wastewater reuse are predominantly oriented towards the planned usage. These are, in turn, regulated by thresholds and guidance values, e. g. for faecal indicator bacteria (e. g. faecal coliforms: E. coli), in widely differing norms and legal provisions specific to the respective countries. In Germany since 2005, small wastewater treatment plants can obtain the discharge class +H by the German Institute for Civil Engineering (DIBt: Deutsches Institut für Bautechnik) if secondary effluents contain less than 100 faecal coliforms (E. coli) per 100 mL. This ensures a safe effluent seepage in karst and water protection areas. Due to the infectious risk caused by a multitude of pathogens (bacteria, viruses, worm eggs, protozoa) which are still contained in wastewater after mechanical-biological treatment, specific disinfection methods are indispensable for their satisfactory reduction. Demands on disinfection methods for wastewater reclamation are quite complex. They should be characterized by a high and constant disinfection efficiency at low or moderate formation of disinfection by-products. The reclaimed wastewater should be able to be stored safely. Moreover, the disinfection method should be technically simple, scaleable, space-saving, subjected to low maintenance and realized at moderate investment and operating costs without applying external toxic chemicals. Established methods in decentralized wastewater disinfection are mainly based on membrane and UV technologies. However, these methods are currently working under high operating costs (high maintenance and cleaning efforts). Furthermore, the high investment costs of the membrane filtration are disadvantageous. In addition, both methods do not provide a disinfection residual. Thus, further research is required for the development and testing of alternative disinfection technologies. Against this background, the applicability of the electrolysis and UV/electrolysis hybrid technology for the decentralized wastewater reclamation was investigated and assessed in this dissertation.
Results have shown that the electrochemical disinfection of biologically treated wastewater represents an efficient method at temperatures of > 6 °C, pH values of < 8.5 and DOC con-centrations of < 22 mg L-1. Under these conditions, an E. coli reduction of four log levels was achieved at a concentration of free chlorine ranging from 0.4 mg L-1 to 0.6 mg L-1 and at an after-reaction time of 15...20 min. However, it becomes simultaneously apparent that low temperatures, high pH values and high DOC concentrations are limiting parameters for this disinfection method to reclaim biologically treated wastewater. A high energy consumption of the electrolysis cell equipped with boron-doped diamond (BDD) electrodes (2...2.6 kWh m-3) represents a further unfavourable effect. Moreover, the undesired formation of chlorate (c = 1.3 mg L-1) and perchlorate (c = 18 mg L-1) at BDD electrodes can be considered as critical, since these disinfection by-products are, amongst others, human-toxicologically relevant. The concentration of adsorbable organically bound halogens (AOX) and trihalomethanes (THMs) proved to be marginal to moderate.
Due to the synergistic effect of the combined application of UV irradiation (primary disinfection method) and electrolysis, the disadvantages of the single methods can be compensated. Decisive drawbacks of UV irradiation are photo and dark repair mechanisms of reversibly damaged bacteria. It was observed that the reactivation of reversibly UV-damaged E. coli even occurs at low temperatures (T = 10 °C) and strongly differing pH values (pH = 5.7...8.1) as well as at low light intensities and in darkness to an extent excluding a safe usage and storage of the reclaimed wastewater. The reactivation processes might be lowered by increased UV fluences. However, this is limited by high concentrations of total suspended solids (TSS). In spite of high UV fluences of > 400 J m-1, no complete removal of E. coli bacteria can be achieved at TSS concentrations of > 17 mg L-1. Therefore, it is indispensable to prevent bacterial reactivation caused by photo and dark repair processes. This topic was studied in the current work by electrochemically produced oxidants using an electrolysis cell positioned downstream of the UV unit. Results have shown that photo and dark reactivation were completely prevented by oxidants in a total concentration of 0.5...0.6 mg L-1 at a TSS concentration of 8...11 mg L-1, at pH values ranging from 5.7 to 8.1 and at temperatures ranging from 10 °C to 30 °C (t = 24....72 h). Even at a high TSS concentration of 75 mg L-1, the reactivation of E. coli (ctotal oxidants = 1.8 mg L-1) and, up to a TSS concentration of 32 mg L-1, the reactivation of total coliforms (except E. coli, ctotal oxidants = 1.0 mg L-1) can be prevented at a high initial germ concentration of 2…3 105 per 100 mL. The lowest energy consumption could be observed when mixed oxide electrodes (MOX electrodes) were applied. This result and the fact that no chlorate and perchlorate were observed at MOX electrodes argue for the application of these electrodes in practice.
All in all, the UV/electrolysis hybrid technology represents an energy-efficient method for reclamation of biologically treated wastewater with TSS concentrations ranging from < 11 to 32 mg L-1 (E = 0.17…0.24 kWh m-3, MOX electrodes). Thereby, the reclaimed wastewater meet the hygienic quality requirements for a multitude of reuse categories starting from agricultural irrigation to urban and recreational reuse. Moreover, the requirements of the discharge class +H (100 faecal coliforms (E. coli) per 100 mL) are complied with reliably. The operational stability of the UV/electrolysis hybrid technology should also be ensured within the required maintenance intervals (t > 6 months). The undesired formation of coverings caused by biofouling processes on quartz glass surfaces could be prevented by electrochemically produced oxidants in a total concentration of 1 mg L-1 within an experimental duration of 5.5 months.
However, the application of the UV/electrolysis hybrid technology is limited by increased particle concentrations and faecal loadings (initial E. coli concentration). The resulting enhanced demand of electrochemically produced oxidants for the prevention of bacterial reactivation results in a considerable increase of the electric charge input and energy consumption.
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Approche multidisciplinaire pour l’amélioration de l’estimation de l’exposition aux sous-produits de désinfection de l’eau en milieu domestique et en piscineCatto, Cyril 01 1900 (has links)
La désinfection de l’eau de consommation et des piscines induit la formation de sous-produits (SPD) potentiellement nocifs pour la santé, parmi lesquels les trihalométhanes (THM), les acides haloacétiques (HAA) et les chloramines (CAM). La difficulté d’estimer l’exposition humaine à ces SPD empêche de cerner précisément les risques sanitaires possiblement associés (i.e., cancérigènes, reprotoxiques, irritatifs). Nos travaux s’articulent autour d’une méthodologie consistant à intégrer des données d’occurrence environnementales à des modèles toxicocinétiques à base physiologique (TCBP) pour améliorer les mesures de l’exposition aux SPD. Cette approche multidisciplinaire veut prendre en compte de manière aussi appropriée que possible les deux composantes majeures des variations de cette exposition : les variations spatio-temporelles des niveaux de contamination environnementale et l’impact des différences inter- et intra-individuelles sur les niveaux biologiques. Cette thèse, organisée en deux volets qui explorent chacun successivement des aspects environnemental et biologique de la problématique, vise à contribuer au développement de cette stratégie innovante d’estimation de l’exposition et, plus généralement, à des meilleures pratiques en la matière.
Le premier volet de la thèse s’intéresse à l’exposition en milieu domestique (i.e., résultant de l’utilisation de l’eau potable au domicile) et est consacré au cas complexe des THM, les plus abondants et volatils des SPD, absorbables par ingestion mais aussi par inhalation et voie percutanée. Les articles I et II, constitutifs de ce volet, documentent spécifiquement la question des variations inter- et intra- journalières de présence des SPD en réseau et de leurs impacts sur les estimateurs de l’exposition biologique. Ils décrivent l’amplitude et la diversité des variations à court terme des niveaux environnementaux, présentent les difficultés à proposer une façon systématique et « épidémiologiquement » pratique de les modéliser et proposent, de manière originale, une évaluation des mésestimations, somme toute modestes, des mesures biologiques de l’exposition résultant de leurs non-prise en compte.
Le deuxième volet de la thèse se penche sur l’exposition aux SPD en piscine, d’un intérêt grandissant au niveau international, et se restreint au cas jugé prioritaire des piscines publiques intérieures. Ce volet envisage, pour quantifier l’exposition dans ce contexte particulier, l’extension de l’approche méthodologique préconisée, élaborée originellement pour application dans un contexte domestique : d’abord, à travers une analyse approfondie des variations des niveaux de contamination (eau, air) des SPD en piscine en vue de les modéliser (article III); puis en examinant, dans le cas particulier du chloroforme, le THM le plus abondant, la possibilité d’utiliser la modélisation TCBP pour simuler des expositions en piscine (article IV). Les résultats mettent notamment en évidence la difficulté d’appréhender précisément la contamination environnementale autrement que par un échantillonnage in situ tandis que la modélisation TCBP apparait, sur le plan toxicologique, comme l’outil le plus pertinent à ce jour, notamment au regard des autres approches existantes, mais qu’il convient d’améliorer pour mieux prédire les niveaux d’exposition biologique.
Finalement, ces travaux illustrent la pertinence et la nécessité d’une approche multidisciplinaire et intégratrice et suggère, sur cette base, les pistes à explorer en priorité pour mieux évaluer l’exposition aux SPD et, in fine, cerner véritablement les risques sanitaires qui en résultent. / Disinfection of drinking and swimming pool waters disinfection is unavoidable but induces the formation of by-products (DBPs), such as trihalomethanes (THMs), haloacetic acids (HAAs) and chloramines (CAMs), that could be harmful to human health. The still challenging DBP exposure assessment prevent their suspected adverse effects (i.e., cancers, adverse pregnancy outcomes, irritations) to be clearly established. A methodology has been conceptualized which consists of integrating environmental occurrence data with physiologically based toxicokinetic (PBTK) modeling to improve DBP exposure assessment. It was designed to allow both spatial and temporal variations of the environmental contamination and the biological impacts of between- and within- individual differences to be accounted for. This thesis comprised of two parts. Each one investigates successively both environmental and biological aspects. The objective is to contribute to the development of an innovative integrated strategy and to the definition of best practices for DBP exposure assessment.
The first part of the thesis, comprising papers I and II, focuses on household exposure (i.e., resulting from drinking water use at home) and on THMs, the most abundant and volatile DBPs that can be absorbed not only by ingestion but also by inhalation and dermal absorption. These two papers investigate particularly the short-term (day-to-day and within-day) variations of THM levels in the drinking water and then their impact on the internal exposure indicators. They described the amplitudes and the diversity of the environmental variations, failed to model them in a systematic and practical way for epidemiological purposes but assessed, for the first time, their impacts on the predicted biological levels which appeared quite low.
The second part concerns the exposure to DBPs in swimming pool which is of a growing international interest. Only the allegedly worrying case of public indoor swimming pool was regarded. This section focuses on the feasibility of using the previously mentioned approach, which was first designed for dealing with household exposure, for DBP exposure assessment in swimming pools. First, Paper III investigated the occurrence and spatial and temporal variations of DBPs in both water and air of swimming pools to model them. Focusing on chloroform, the most abundant THM, Paper IV examined the ability and reliability of PBTK modeling to simulate various swimming pool exposure events and predict the resulting biological levels in individuals. The results show, among other things, the difficulty of explaining precisely the environmental contamination and point out the necessity to carry out a minimal in situ sampling to monitor the environmental levels of DBPs. Compared to other approaches, PBTK modeling is a powerful but still to be improved tool for predicting swimming pool exposure.
Eventually, these works underline the relevance and the necessity of a multidisciplinary and integrating approach for better estimating exposure to DBPs and therefore health risks. Further issues that should be addressed are recommended.
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FARINHAS DE RESÍDUOS DE ABATEDOUROS AVÍCOLAS EM DIFERENTES GRAUS DE PROCESSAMENTO EM RAÇÕES PRÉ-INICIAIS E INICIAIS DE FRANGOS DE CORTE / Poultry by-products from abattoir plants in different processing methods in pre-starter and starter rations.LABOISSIERE, Michele 28 August 2008 (has links)
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Previous issue date: 2008-08-28 / In this experiment, the inclusion of viscera and bone meal (FVO) and
feather and blood meal (FPS) according to its processing grade was evaluated in
broiler pre-starter and starter rations. The experiments were conducted in the
poultry experimental facilities of the Veterinary College of the Federal University of
Goiás (EV/UFG), located in Goiânia, Brazil. A total of four experiments were
carried out to evaluate performance, digestibility and intestinal biometry of broilers
fed diets containing viscera and bone meal (FVO) with different moisture levels in
processing and feather and blood meal (FPS) with different pressing levels in
processing in pre-starter (one to seven days of age) and starter (eight to 21 days
of age). In the first experiment, 9% inclusion of FVO with different moisture levels
at processing (4, 5 and 6%) in pre-starter rations. In the second experiment, the
same moisture levels of FVO were analyzed for starter rations. In the third
experiment, 9% inclusion of FPS with different hydrolysis pressing at processing
(2,0, 2,5 e 3,0 kg/cm2) in pre-starter ration was tested. In the experiment 4, the
same hydrolysis pressing levels were tested for FPS but now at starter rations.
The experiment was conducted in a randomized block design, and the criteria to
the blocks determination was the battery-cage, with four treatments and five
replications of 12 birds each, in a total of 20 experimental units. The statistical
analysis was done using UFV/SAEG (2000) and means compared as Tukey test
(%5). Variables tested were: live weight, weight gain, feed intake, feed-to-gain
ratio, dry matter, nitrogen and ether extract digestibility, dry matter, nitrogen and
ether extract retention and biometric indexes of digestive organs. The results
indicated that 9% of FVO or FPS didn t affect the performance results. To prestarter
phases, the best results were obtained with diets processed with FVO with
5% moisture and FPS with 2,5 kg/cm2 of hydrolysis processing. For starter rations,
FVO or FPS didn t affect broiler performance. The poultry by-products processed
for animal feeding can be used without performance lost but is important to know
the nutritional processing of these ingredients. / Neste trabalho avaliou-se a inclusão de farinhas de vísceras e ossos
(FVO) e farinhas de penas e sangue (FPS) com diferentes graus de
processamento de fabricação nas dietas pré-iniciais e iniciais de frangos de corte.
Os experimentos foram conduzidos no aviário experimental do Setor de Avicultura
da Escola de Veterinária da Universidade Federal de Goiás (EV/UFG) em Goiânia
GO. Foram realizados quatro experimentos para avaliar o desempenho, a
digestibilidade e a biometria intestinal em frangos alimentados com dietas
contendo farinhas de vísceras e ossos (FVO) com diferentes graus de umidade
das farinhas de penas e sangue (FPS) com diferentes pressões de hidrólise no
processamento nas fases pré-inicial (um a sete dias de idade) e inicial (oito a 21
dias de idade). No primeiro experimento avaliou-se a inclusão de 9% de farinha
de vísceras e ossos (FVO) com diferentes graus de umidade no processamento
(4, 5 e 6%) na ração pré-inicial. No segundo experimento avaliou-se a inclusão de
9% de FVO com diferentes graus de umidade no processamento (4, 5 e 6%) na
ração inicial. No terceiro experimento avaliou-se a inclusão de 9% de farinha de
penas e sangue (FPS) com diferentes pressões de hidrólise no processamento
(2,0, 2,5 e 3,0 kg/cm2) na ração pré-inicial. No quarto experimento avaliou-se a
inclusão de 9% de FPS com diferentes pressões de hidrólise no processamento
(2,0, 2,5 e 3,0 kg/cm2) na ração inicial. O delineamento experimental aplicado foi
de blocos ao acaso e o critério de distribuição do bloco foi o andar da bateria, com
quatro tratamentos e cinco repetições de 12 aves cada, totalizando 20 unidades
experimentais. As análises estatísticas foram realizadas utilizando o programa da
UFV/SAEG (2000) e o teste de Tukey a 5% de probabilidade para comparação
das médias. As variáveis avaliadas foram: peso vivo, ganho de peso, consumo de
ração, índice de conversão alimentar, digestibilidade de matéria seca, do
nitrogênio e do extrato etéreo, retenção da matéria seca, do nitrogênio e do
extrato etéreo e os índices biométricos dos órgãos. Após análise dos resultados,
observou-se que 9,0% de inclusão de FVO e 9% de FPS, utilizadas isoladamente
na dieta, não afetou o desempenho das aves. Para as fases pré-iniciais os
melhores resultados de metabolismo de nutrientes foram obtidos com as dietas
processadas com FVO a 5% de umidade e FPS a 2,5 kg/cm2 de pressão de
hidrólise e para as dietas iniciais o processamento das farinhas não alterou
significativamente o desempenho das aves. Concluiu-se que as farinhas de
resíduos de abatedouros avícolas podem ser utilizadas sem prejudicar o
desempenho das aves desde que se conheça seu processamento e o valor
nutricional desejado desses ingredientes.
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Možnosti využití vláken na bázi druhotných a snadnoobnovitelných surovin při výrobě pokročilých stavebních materiálů / Possibilities of utilization fiber-based and secondary easy-renewable raw sources in the production of lightweight building materialsHoráková, Lucie January 2018 (has links)
The diploma thesis dealt with the possibilities of of utilization fiber-based and secondary easy-renewable raw sources in the production of lightweight building materials. The theoretical part includes literature search of the researches, which dealt with this issue. Appropriate sources of fibers were selected within the theoretical part and the findings were used in the practical part of the thesis. Within the practical part laboratory measurements and subsequent selection of the most suitable fibers were performed. Laboratory measurements and subsequent selection of the most suitable fibers were performed in the practical part. Subsequently, designs of thermal insulating plasters (with the possibility of using as repairing plasters) were made on the basis of lightweight glass aggregate, to which the production of test specimens was connected. Laboratory tests were performed on fresh and hardened mortars and subsequently evaluated. In conclusion, an economic evaluation and assessment of the competitiveness of the proposed plasters was carried out.
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Innovative Desinfektionsverfahren zur Brauchwassergewinnung in der dezentralen Abwasserbehandlung - Elektrolyse und UV/Elektrolyse-HybridtechnikHaaken, Daniela 24 April 2015 (has links)
According to estimates of the United Nations Environment Programme (UNEP), more than 1.8 billion people will be living in countries or regions with absolute water scarcity by 2025. The pressure on water resources is increased not only in arid and semiarid regions, but also in fast growing megacities around the world as a result of, amongst other factors, the changing nutritional and consumer behavior (rising living standards). Over 90 % of the annual water consumption of the newly industrializing and developing countries in the arid and semiarid climate zone is used for agricultural irrigation to ensure the nutrition of the population. Thus, since the beginning of the 20th century, the planned/controlled reuse of wastewater has developed into a central task of the sustainable water resources management. Wastewater represents a valuable resource in view of its composition (e. g. nutrients P, N for soil fertilizing) and its reliable, weather-independent availability in every household. The establishment of a closed-loop water management can enhance the efficiency of water usage. Therefore, activities in research and development are currently focused on decentralized and semi-centralized concepts, since their structures offer better conditions for the establishment of closed-loop systems and innovations in wastewater technology can be implemented more easily.
In general, the hygienic quality requirements for wastewater reuse are predominantly oriented towards the planned usage. These are, in turn, regulated by thresholds and guidance values, e. g. for faecal indicator bacteria (e. g. faecal coliforms: E. coli), in widely differing norms and legal provisions specific to the respective countries. In Germany since 2005, small wastewater treatment plants can obtain the discharge class +H by the German Institute for Civil Engineering (DIBt: Deutsches Institut für Bautechnik) if secondary effluents contain less than 100 faecal coliforms (E. coli) per 100 mL. This ensures a safe effluent seepage in karst and water protection areas. Due to the infectious risk caused by a multitude of pathogens (bacteria, viruses, worm eggs, protozoa) which are still contained in wastewater after mechanical-biological treatment, specific disinfection methods are indispensable for their satisfactory reduction. Demands on disinfection methods for wastewater reclamation are quite complex. They should be characterized by a high and constant disinfection efficiency at low or moderate formation of disinfection by-products. The reclaimed wastewater should be able to be stored safely. Moreover, the disinfection method should be technically simple, scaleable, space-saving, subjected to low maintenance and realized at moderate investment and operating costs without applying external toxic chemicals. Established methods in decentralized wastewater disinfection are mainly based on membrane and UV technologies. However, these methods are currently working under high operating costs (high maintenance and cleaning efforts). Furthermore, the high investment costs of the membrane filtration are disadvantageous. In addition, both methods do not provide a disinfection residual. Thus, further research is required for the development and testing of alternative disinfection technologies. Against this background, the applicability of the electrolysis and UV/electrolysis hybrid technology for the decentralized wastewater reclamation was investigated and assessed in this dissertation.
Results have shown that the electrochemical disinfection of biologically treated wastewater represents an efficient method at temperatures of > 6 °C, pH values of < 8.5 and DOC con-centrations of < 22 mg L-1. Under these conditions, an E. coli reduction of four log levels was achieved at a concentration of free chlorine ranging from 0.4 mg L-1 to 0.6 mg L-1 and at an after-reaction time of 15...20 min. However, it becomes simultaneously apparent that low temperatures, high pH values and high DOC concentrations are limiting parameters for this disinfection method to reclaim biologically treated wastewater. A high energy consumption of the electrolysis cell equipped with boron-doped diamond (BDD) electrodes (2...2.6 kWh m-3) represents a further unfavourable effect. Moreover, the undesired formation of chlorate (c = 1.3 mg L-1) and perchlorate (c = 18 mg L-1) at BDD electrodes can be considered as critical, since these disinfection by-products are, amongst others, human-toxicologically relevant. The concentration of adsorbable organically bound halogens (AOX) and trihalomethanes (THMs) proved to be marginal to moderate.
Due to the synergistic effect of the combined application of UV irradiation (primary disinfection method) and electrolysis, the disadvantages of the single methods can be compensated. Decisive drawbacks of UV irradiation are photo and dark repair mechanisms of reversibly damaged bacteria. It was observed that the reactivation of reversibly UV-damaged E. coli even occurs at low temperatures (T = 10 °C) and strongly differing pH values (pH = 5.7...8.1) as well as at low light intensities and in darkness to an extent excluding a safe usage and storage of the reclaimed wastewater. The reactivation processes might be lowered by increased UV fluences. However, this is limited by high concentrations of total suspended solids (TSS). In spite of high UV fluences of > 400 J m-1, no complete removal of E. coli bacteria can be achieved at TSS concentrations of > 17 mg L-1. Therefore, it is indispensable to prevent bacterial reactivation caused by photo and dark repair processes. This topic was studied in the current work by electrochemically produced oxidants using an electrolysis cell positioned downstream of the UV unit. Results have shown that photo and dark reactivation were completely prevented by oxidants in a total concentration of 0.5...0.6 mg L-1 at a TSS concentration of 8...11 mg L-1, at pH values ranging from 5.7 to 8.1 and at temperatures ranging from 10 °C to 30 °C (t = 24....72 h). Even at a high TSS concentration of 75 mg L-1, the reactivation of E. coli (ctotal oxidants = 1.8 mg L-1) and, up to a TSS concentration of 32 mg L-1, the reactivation of total coliforms (except E. coli, ctotal oxidants = 1.0 mg L-1) can be prevented at a high initial germ concentration of 2…3 105 per 100 mL. The lowest energy consumption could be observed when mixed oxide electrodes (MOX electrodes) were applied. This result and the fact that no chlorate and perchlorate were observed at MOX electrodes argue for the application of these electrodes in practice.
All in all, the UV/electrolysis hybrid technology represents an energy-efficient method for reclamation of biologically treated wastewater with TSS concentrations ranging from < 11 to 32 mg L-1 (E = 0.17…0.24 kWh m-3, MOX electrodes). Thereby, the reclaimed wastewater meet the hygienic quality requirements for a multitude of reuse categories starting from agricultural irrigation to urban and recreational reuse. Moreover, the requirements of the discharge class +H (100 faecal coliforms (E. coli) per 100 mL) are complied with reliably. The operational stability of the UV/electrolysis hybrid technology should also be ensured within the required maintenance intervals (t > 6 months). The undesired formation of coverings caused by biofouling processes on quartz glass surfaces could be prevented by electrochemically produced oxidants in a total concentration of 1 mg L-1 within an experimental duration of 5.5 months.
However, the application of the UV/electrolysis hybrid technology is limited by increased particle concentrations and faecal loadings (initial E. coli concentration). The resulting enhanced demand of electrochemically produced oxidants for the prevention of bacterial reactivation results in a considerable increase of the electric charge input and energy consumption.
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Uticaj oksidacionih procesa na bazi ozona, vodonik-peroksida i UV zračenja na sadržaj i reaktivnost prirodnih organskih materija u vodi / The influence of oxidation processes based on ozone, hydrogen peroxide and UV irradiation on the content and reactivity of natural organic matter in waterPetronijević Mirjana 28 August 2019 (has links)
<p>Cilj istraživanja u okviru ove doktorske disertacije je utvrđivanje efekata različitih<br />oksidacionih procesa na bazi ozona, vodonik-peroksida i UV zračenja na sadržaj i reaktivnost prirodnih organskih materija (POM) u različitim vodenim matriksima. Ispitivanja su sprovedena na a) podzemnoj vodi sa teritorije Kikinde i Temerina (prirodni matriks) i b) sintetičkom vodenom matriksu (rastvoru komercijalno dostupne huminske kiseline), koji se među sobom razlikuju po sastavu i strukturi prisutne POM i sadržaju bromida. Za oksidacioni proces (ozonizacija, UV fotoliza, oksidacija sa H<sub> 2</sub>O<sub>2</sub>, kombinovani O <sub>3 </sub>/UV proces i kombinovani H <sub>2</sub>O<sub>2</sub><br />/UV proces) pojedinačno ispitan je uticaj različitih doza oksidanata i reakcionih uslova.Posebna pažnja posvećena je ispitivanju uticaja navedenih tretmana na<br />formiranje neorganskog bromata, kao i uticaja na sadržaj prekursora dezinfekcionih nusproizvoda nakon hlorisanja (THM, HAA, HAN, HK i CP).<br />Analiza hemijskih parametara sintetičkog matriksa (5,44±0,30 mg C/l; 0,255±0,015 cm<sup> -1</sup> ; 4,68±0,41 lm<sup> -1</sup> mg <sup>-1 </sup>) pokazuje da u njemu preovladavaju huminnske materije visoke hidrofobnosti. Visok sadržaj POM pretežno hidrofobnog karaktera je zabeležen i u vodi iz Kikinde (5,170,72 mg C/l; 0,2010,001 cm <span id="cke_bm_192S" style="display: none;"> </span><span id="cke_bm_190S" style="display: none;"> </span><sup>-1</sup><span id="cke_bm_192E" style="display: none;"> </span><span id="cke_bm_190E" style="display: none;"> </span> ; 3,88±0,70 lm<span id="cke_bm_193S" style="display: none;"> </span><sup> -1</sup><span id="cke_bm_193E" style="display: none;"> </span> mg<sup> -1</sup> ), dok je sadrža<span id="cke_bm_194E" style="display: none;"> </span>j POM u sirovoj vodi iz Temerina (2,060,38 mg C/l; 0,0500,001 cm<span id="cke_bm_203S" style="display: none;"> </span><span id="cke_bm_201S" style="display: none;"> </span><sup> -1</sup><span id="cke_bm_203E" style="display: none;"> </span><span id="cke_bm_201E" style="display: none;"> </span> ; 2,43±0,21 lm <span id="cke_bm_204S" style="display: none;"> </span><sup>-1</sup><span id="cke_bm_204E" style="display: none;"> </span> mg <sup>-1</sup><span id="cke_bm_205E" style="display: none;"> </span><span id="cke_bm_202E" style="display: none;"> </span><span id="cke_bm_191E" style="display: none;"> </span><br />) značajno niži i preovladavaju POM hidrofilnog karaktera. Veći stepen hidrofobnosti sintetičkog matriksa u poređenju sa prirodnim matriksima, rezultovao je i većom reaktivnosti organske materije sa hlorom, što se može zaključiti na<br />osnovu visokih vrednosti PFDBP nakon hlorisanja. Vrednost PFTHM u sintetičkom matriksu iznosi 544±85,9 µg/l, dok je PFTHM u kikindskoj i temerinskoj sirovoj vodi znatno niži (279±32,3 i 180±44,0 µg/l, respektivno). Vrednost PFHAA u sintetičkom matriksu iznosi 484±77,5 µg/l, dok je PFHAA u kikindskoj 244±11,1 µg/l i u temerinskoj vodi 165±32,5 µg/l. Sadržaj HK (8,05±3,63 µg/l sintetički matriks; 14,91,38 µg/l Kikinda; 7,400,25 µg/l Temerin) je znatno niži u poređenju sa prekursorima THM i HAA, dok prekursori HAN i hlorpikrina nisu detektovani u sirovoj vodi. Nusproizvodi koji se dominantno formiraju u svim ispitivanim vodenim matriksima su hlorovani THM i HAA, dok se bromovani DBPformiraju u znatno nižim koncentracijama. Zastupljenost bromovanih DBP u temerinskoj vodi<br />je znatno veći u poređenju sa vodom iz Kikinde, kao rezultat prisustva veće koncentracije bromida u sirovoj vodi (0,05±0,01 mg Br -/l Temerin; 0,03±0,01 mg Br<br />-/l Kikinda). Ispitivanjem uticaja oksidacionih procesa (UV fotolize, ozonizacije, oksidacije vodonik-peroksidom) na sadržaj i reaktivnost POM u ispitivanim vodenim matriksima utvrđeno je da tretman vode UV zračenjem i vodonik-peroksidom, kada se primenjuju kao samostalan tretman, ne pokazuju značajnu efikasnost u smanjenju sadržaja POM.Tretman vode ozonom se pokazao kao veoma efikasan u uklanjanju POM i u smanjenju sadržaja prekursora DBP kod svih ispitivanih vodenih matriksa, kao rezultat smanjenja reaktivnosti POM ka formiranju ovih DBP. Smanjenje sadržaja POM u vodi tokom tretmana raste sa povećanjem primenjene doze ozona, pri čemu se najbolji rezultati postižu pri najvećoj primenjenoj dozi od 3,0 mg O 3/mg DOC (do 32% DOC, 92% UV254 sintetički matriks; do 17% DOC, 76% UV 254 Kikinda; do 15% DOC i 66% UV254 Temerin). U sintetičkom matriksu najveće smanjenje PFTHM (za 76%) i PFHAA (za 80%) u odnosu na sadržaj u sirovoj vodi se postiže pri dozi od 1,0 mg O<sub>3 </sub>/mg DOC. Najveće smanjenje PFTHM (za 38%)<br />i PFHAA (za 42%) u vodi iz Kikinde postiže se pri dozi od 3,0 mg O <sub>3 </sub>/mg DOC. U vodi iz Temerina najveće smanjenje PFTHM (za 27%) je pri dozi od 3,0 mg O <sub>3</sub> /mg DOC, dok se za smnjenje PFHAA (za 54%) najbolje pokazala doza od 1,0 mg O<br />3 /mg DOC. Sadržaj prekursora HK i HAN (temerinska voda) je veoma nizak nakon tretmana. Tretman vode ozonom vodi ka formiranju DBP sa više supstituisanih atoma broma, dok u vodama sa srednjim sadržajem bromida (50 µg Br -/l) dovodi do formiranja bromata. Kombinacijom ozonizacije sa UV zračenjem se značajno može pospešiti efiksnost uklanjanja POM postignuta primenom samostalne ozonizacije. Najveće smanjenje sadržaja POM u sintetičkom matriksu (za 85% DOC, 98% UV254 i 87% SUVA), u vodi iz Kikinde (za<br />23% DOC, 83% UV 254, 77% SUVA), i vodi iz Temerina (za 15% DOC, 80% UV<br />254 i 75% SUVA), u odnosu na vrednosti u netretiranoj vodi postignuto je pri najvećoj primenjenoj dozi od 3,0 mg O<sub> 3</sub> /mg DOC i 6000 mJ/cm 2 . Efikasnost procesa raste u vodama u kojima preovladavaju POM veće hidrofobnosti. MeĎutim, iako se O<sub> 3</sub> /UV procesom postiže visok stepen smanjenja PFTHM u sintetičkom matriksu se najbolje pokazao tretman ozonom (1,0 mg O3/mg DOC), dok se najveće smanjenje PFHAA (82%) postiže pri dozi ozona od 1,0 mg O<sub>3/</sub>mg DOC i UV zračenja od 6000 mJ/cm <sup>2 .</sup> U vodi iz Kikinde se PFTHM smanjuje za 50% pri dozi od 3,0 mg O <sub>3</sub>/mg DOC i 6000 mJ/cm 2 , dok se u slučaju uklanjanja prekursora<br />HAA ozonizacija pokazala kao superiorniji proces. U vodi iz Temerina se u pogledu uklanjanja prekursora THM i HAA ozonizacija pokazala kao optimalan proces. Visok alkalitet prirodnih voda inhibira radikalski mehanizam u toku AOP i favorizuje oksidaciju POM molekulskim ozonom. Prekursori HK se formiraju u veoma niskim koncentracijama i njihov sadržaj ne varira značajno tokom tretmana. U prirodnim matriksima tokom AOP pri dozi ozona od 3,0 mg O<sub>3</sub> /mg DOC dolazi do formiranja HAN, međutim, nije uočen jasan trend sa povećanjem doze UV zračenja. Tretman doprinosi formiranju bromovanih vrsta THM, dok se tokom AOP pri najvećoj dozi ozona od 3,0 mg O<sub>3</sub> /mg DOC formiraju bromovani HAN.<br />Najveće smanjenje sadržaja POM primenom kombinacije oksidacije sa H <sub>2</sub>O<sub>2</sub><br />i UV zračenja u sintetičkom matriksu (za do 17% DOC, 70% UV 254 ), u vodi iz Kikinde (za do 22% DOC, 53% UV<sub>254</sub>), i vodi iz Temerina (za do 7% DOC, 68% UV<br /><sub>254 </sub>), u odnosu na vrednosti u sirovoj vodi, se postižu pri dozi H <sub>2</sub>O<sub>2</sub> i UV zračenja od 3,0 mg H<sub>2</sub>O<sub>2</sub>/mg DOC i 6000 mJ/cm <sup>2</sup> .<br />Najveće smanjenje PFTHM od 54% u sintetičkom matriksu se postiže pri dozi od 0 mg H<sub>2</sub>O<sub>2</sub>/mg DOC i 6000 mJ/cm <sup>2</sup> , dok se smanjenje PFHAA (za 35%) postiže primenom doze vodonik-peroksida i UV zračenja od 1,0 mg H <sub>2</sub>O<sub>2</sub> /mg DOC i 3000 mJ/cm <sup>2</sup> . U vodi izKikinde H<sub>2</sub>O<sub>2</sub> /UV proces ne utiče značajno na sadržaj prekursora THM, dok se najveće smanjenje PFHAA (za 35%) postiže pri dozi od 3,0 mg H<sub> <span id="cke_bm_235S" style="display: none;"> </span>2<span id="cke_bm_235E" style="display: none;"> </span></sub>O<sub>2</sub>/mg DOC i 600 mJ/cm <sup>2</sup> .H<span id="cke_bm_184S" style="display: none;"> </span><sub>2</sub><span id="cke_bm_184E" style="display: none;"> </span>O<sub>2</sub><span id="cke_bm_185E" style="display: none;"> </span>/UV proces dovodi do smanjenja PFTHM u Temerinskoj vodi za 74% pri dozi od 3,0 mg H<sub>2</sub>O<sub>2</sub>/mg DOC i 600 mJ/c<span id="cke_bm_236E" style="display: none;"> </span>m <sup>2</sup> , dok primenjeni tretman ne pokazuje značajan uticaj na<br />PFHAA. Prekursori HK su detektovani u sintetičkom matriksu i temerinskoj vodi u niskim koncentracijama. U temerinskoj vodi nakon AOP pri dozi vodonik-peroksida od 3,0 mg H<sub>2</sub>O<sub>2</sub> /mg DOC dolazi do formiranja HAN i hlorpikrina. Primenjeni tretman vodi ka formiranju bromovanih DBP. Svi rezultati dobijeni u toku istraživanja ukazuju na neophodnost optimizacije procesa u tretmanu ispitivanih vodenih matriksa i određivanja optimalnog procesa uzimajući u obzir<br />karakteristika sirove vode i efikasnost koja se želi postići.Kombinacijom dva i više konvencionalnih tretmana i optimizacijom reakcionih uslova može se postići visoka efikasnost uklanjanja POM, kao i ciljano uklanjanje prekursorskog materijala odabranih DBP, međutim tretman vode ozonom pri dozi od 1,0 mg O<sub>3</sub><br />/mg DOC se pokazao kao optimalan proces.</p> / <p>The aim of the research of this PhD thesis was to determine the effects of various oxidation processes based on ozone, hydrogen peroxide and UV irradiation on the content and reactivity of natural organic matter (NOM) in different water matrices. The tests were carried out on a) groundwater from the territory of Kikinda and Temerin (natural matrix) and b) synthetic aqueous matrix (solution of commercially available humic acid), which differ in the composition and structure of NOM present and the content of bromide. For the oxidation process (ozonation, UV photolysis, oxidation with H 2O2 , combined O 3 /UV process and combined H 2O2 /UV process), the influence of different doses of oxidants and reaction conditions was examined individually. Particular attention was paid to the influence of the above treatment on the formation of inorganic bromate, as well as the effect on the content of precursors of disinfectant by-products after chlorination (THM, HAA, HAN, HK and CP).Analysis of the chemical parameters of the synthetic matrix (5.44±0.30 mg C/L; 0.255±0.015 cm -1 ; 4.68±0.41 lm -1 mg -1 ) shows that the high-hydrophobic humic compounds predominate in this water. Also, high NOM content of predominantly hydrophobic character was recorded in Kikinda water (5.170.72 mg C/L; 0.2010.001 cm -1 ; 3.88±0.70 lm -1 mg -1 ), while NOM content in raw water from Temerin (2.060.38 mg C/L; 0.0500.001 cm -1 ; 2.43±0.21 lm -1 mg -1 ) significantly lower and predominate NOM of hydrophilic character. A higher degree of hydrophobicity of the synthetic matrix in comparison with natural matrices, resulted in higher reactivity of organic matter with chlorine, which can be concluded on the basis of high PFDBP values after chlorination. The PFTHM value in the synthetic matrix was 544±85.9 µg/L, while the PFTHM in the raw waters from Kikinda and Temerin was significantly lower (279±32.3 and 180±44.0 µg/L, respectively). The PFHAA value in the synthetic matrix was 484±77.5 µg/L, while PFHAA in the Kikinda water was 223 244±11.1 µg/L and in the Temerin water was 165±32.5 µg/L. The content of precursors of HK (8.05±3.63 µg/L synthetic matrix; 14.91.38 µg/L Kikinda; 7.400.25 µg/L Temerin) was significantly lower compared to precursors of THMs and HAAs, while precursors of HANs and chloropicrin were not detected in raw water. The by- products that were predominantly formed in all the tested water matrices were chlorinated THMs and HAAs, while the brominated DBPs were formed at substantially lower concentrations. The presence of brominated DBPs in Temerine water were significantly higher compared to Kikinda water as a result of the presence of higher bromide content in raw water (0.05±0.01 mg Br -/L Temerin; 0.03±0.01 mg Br -/L Kikinda). By examining the influence of oxidation processes (UV photolysis, ozonation,hydrogen peroxide oxidation) on the content and reactivity of NOM in the tested water matrix, it was found that the UV irradiation and treatment by hydrogen peroxide, when used as an independent treatment, did not show significant efficacy in reducing the NOM content. Water treatment by ozone proved to be very effective in eliminating NOM and reducing the content of DBP precursors in all tested water matrices, as a result of the reduction of NOM reactivity to the formation of these DBPs. Reduction of NOM content in water during treatment increased with increasing the applied dose of ozone, with the best results achieved at the highest dosage of 3.0 mg O 3/mg DOC (up to 32% DOC, 92% UV 254 synthetic matrix, up to 17% DOC, 76% UV 254 Kikinda, up to 15% DOC and 66% UV254 Temerin). In the synthetic matrix the highest reduction in PFTHM (76%) and PFHAA (by 80%) compared to raw water content was achieved at a dosage of 1.0 mg O 3/mg DOC. The highest reduction in PFTHM (38%) and PFHAA (42%) in Kikinda water was achieved at a dose of 3.0 mg O3 /mg DOC. In Temerin water, the highest reduction in PFTHM (27%) was at a dose of 3.0 mg O 3/mg DOC, while the dose of 1.0 mg O3 /mg DOC was best shown for removing PFHAA (by 54%). The content of the precursors of HKs and HANs (Temerin water) was very low after treatment. Water treatment by ozone led to the formation of DBPs with more substituted bromine atoms, while in waters with a mean bromide content (50 μg Br -/L) led to bromate formation.Combination of ozonation with UV irradiation can greatly accelerate the effectiveness of NOM removal achieved by the use of ozonation alone. The highest reduction in NOM content in the synthetic matrix (by 85% DOC, 98% UV 254 and 87% SUVA), in Kikinda water (by 23% DOC, 83% UV 254 , 77% SUVA) and water from Temerin (by 15% DOC, 80% UV 254 and 75% SUVA), compared to the values in raw water, was achieved at the highest dose of 3.0 mg O 3 /mg DOC and 6000 mJ/cm 2 . The efficiency of the process was growing in the waters where NOM predominates of hydrophobicity. Although the O 3 /UV process achieved a high degree of reduction in PFTHM in the synthetic matrix the ozonation (1.0 mg O3 /mg DOC) was proved as more efficient, while the highest reduction in PFHAA (82%) was achieved at a ozone dose of 1.0 mg O 3/mg DOC and UV irradiation of 6000 mJ/cm 2 . In the water from Temerin, in case to removal of precursors of THM and HAA, ozonation was proved to be an optimal process. High alkalinity of natural waters inhibits the radical mechanism during AOP and favors NOM oxidation with molecular ozone. HKs precursors were formed at very low concentrations and their content did not vary significantly during the treatment. In natural matrices during the AOP at a ozone dose of 3.0 mg O3 /mgDOC, HANs were formed, however, there was no clear trend with increasing UV irradiation. The treatment contributed to the formation of brominated THM species, while during the AOPs, brominated HANs were formed at the maximum dose of ozone of 3.0 mg O3/mg DOC. 224 The largest decrease in NOM content by the combination of oxidation with H2O2 and UV irradiation in the synthetic matrix (for up to 17% DOC, 70% UV 254 ), in Kikinda water (up to 22% DOC, 53% UV 254), and water from Temerin (7% DOC, 68% UV 254 ), compared to the values in raw water, were obtained at a dose of H 2O2 and UV irradiation of 3.0 mg O3 /mg DOC and 6000 mJ/cm 2 . The highest PFTHM reduction of 54% in the synthetic matrix was achieved at a dosage of 1.0 mg H2O2/mg DOC and 6000 mJ/cm 2 , while a decrease in PFHAA (35%) was achieved using a dose of hydrogen peroxide and UV irradiation of 1.0 mg H2O2/mg DOC and 3000 mJ/cm 2 . In the water from Kikinda, the H2O2 /UV process did not significantly affect on the THM precursors content, while the highest reduction in PFHAA (35%) was achieved at a dose of 3.0 mg H2O2/mg DOC and 600 mJ/cm 2 . The H 2O2 /UV process led to a decrease in PFTHM in the Temerin water by 74% at a dose of 3.0 mg 2O2 /mg DOC and 600 mJ/cm 2 , whereas the treatment applied had no significant effect on PFHAA. HKs precursors were detected in synthetic matrix and the Temerin water at low concentrations. In the water after the AOP at a dose of 3.0 mg H 2O2 /mg DOC of hydrogen peroxide, HANs and chloropicrin were formed. The applied treatment led to the formation of brominated DBPs.<br />All the results obtained during the research indicate the necessity of optimization the process in the treatment of the examined water matrices and determination of the optimal process taking into account the characteristics of raw water and the efficiency to be achieved. By combining two or more conventional treatments and optimizing the reaction conditions, high NOM removal efficiency can be achieved, as well as removal of the targeted precursor material of the selected DBPs, but the treatment of ozone water at a dose of 1.0 mg O3 /mg DOC was proved to be an optimal process.</p>
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Emerging Photochemical Processes Involving Iron for Wastewater TreatmentSciscenko, Iván Matías 22 November 2021 (has links)
Tesis por compendio / [ES] Los procesos (foto-)Fenton fueron empleados para degradar fluoroquinolonas (FQ) (una clase de antibióticos sintéticos considerados CEC) como contaminantes modelo en diferentes condiciones: pH (3 - 8), concentración de contaminante (3 - 300 μM), número de FQ presentes (1, 3 y 5), y matrices de agua (agua ultrapura, salina y de WWTP simulada). Los experimentos se realizaron a escala banco y planta piloto, empleando luz solar (simulada y real) e irradiaciones con luz ultravioleta. Las velocidades de degradación de los contaminantes obtenidas con procesos tipo-Fenton se compararon con las análogas de fotólisis, fotocatálisis heterogénea y H2O2/UV. En igualdad de condiciones, solo a través del proceso foto-Fenton se logró una mineralización significativa de las FQs. En aquellos casos en los que el carbono orgánico total no mostró una disminución considerable, la razón se atribuye a la liberación de subproductos de oxidación.
EEM-PARAFAC ha demostrado ser una técnica económica, veloz y que no requiere del uso de reactivos, para seguir simultáneamente la eliminación de la degradación de hasta 5 FQs fluorescentes presentes en una misma muestra, en presencia de interferencias sin calibrar, y obtener información sobre las posibles estructuras moleculares de los intermediarios de reacción. Los resultados indicaron que la fotólisis por sí sola no es capaz de producir cambios importantes en la estructura de las FQs, mientras que con (foto-)Fenton sí que se observó una notable disminución de los scores de los componentes PARAFAC asociados con los compuestos del tipo FQ. Los ensayos de zona de inhibición empleando E. coli mostraron que la actividad antibiótica disminuyó en paralelo con la desintegración de todos los componentes PARAFAC relacionados con las FQs y subproductos similares a estas.
El otro aspecto importante de la tesis fue el uso de procesos Fenton basados en ZVI. Algunos CEC, como los compuestos nitroaromáticos, exhiben tasas de degradación lentas incluso cuando son degradadas por una AOP. El desarrollo de trenes de tratamiento ZVI para la degradación de contaminantes ha despertado un gran interés en los últimos años. Este enfoque consiste en un primer pretratamiento solo con ZVI (es decir, reducción, deshalogenación), seguido del proceso Fenton aprovechando los iones de hierro liberados en el primer paso. Con el fin de analizar las posibles ventajas e inconvenientes de esta estrategia en las aplicaciones de tratamiento de aguas residuales, se ha estudiado este enfoque empleando micropartículas de ZVI (mZVI) comerciales utilizando ácido p-nitrobenzoico (PNBA) como contaminante modelo. Se analizó el efecto de la cantidad inicial de mZVI, H2O2, pH, conductividad, aniones y oxígeno disuelto. Utilizando agua natural en condiciones aeróbicas, pH inicial 3,0, y adicionando 1,4 g/L de mZVI, se consiguió en 2 h una reducción del 83% de PNBA 6 μM en ácido p-aminobenzoico (PABA). Se investigó también la conveniencia de separar las mZVI después de la fase reductora (antes de la etapa Fenton) así como la reutilización de las mZVI. El paso de Fenton contra el PABA, más reactivo que PNBA, requirió 50 mg/L de H2O2 para lograr una eliminación de más del 96% en 15 min a pH 7,5 (pH final del pretratamiento reductivo). Las mZVI reutilizadas fueron efectivas por lo menos por un ciclo completo (reducción/oxidación). Este enfoque puede ser interesante para tratar aguas residuales que contienen contaminantes inicialmente resistentes al radical hidroxilo (HO), pero fácilmente reducibles, pudiendo disminuir su carga tóxica y aumentar su reactividad para un paso de oxidación posterior. / [CA] Fenton i foto-Fenton van ser emprats per a degradar fluoroquinolones (FQ) (una classe d'antibiòtics sintètics considerats CEC) com a contaminants model en diferents condicions: pH (3 - 8), concentració de contaminant (3 - 300 μM), nombre de FQ presents (1, 3 i 5), i matriu d'aigua (aigua ultrapura, salada i de WWTP simulada). Els experiments es van realitzar a escala de laboratori i planta pilot, emprant llum solar (simulada i real) i irradiacions amb llum ultraviolada. Les velocitats de degradació de contaminants obtingudes amb processos tipus-Fenton es van comparar amb fotòlisi, fotocatàlisi heterogènia i H2O2/UV. En igualtat de condicions, només a través del procés foto-Fenton es va aconseguir una mineralització significativa de FQ. En aquells casos en els quals el carboni orgànic total no va mostrar una disminució considerable, la raó s'atribueix a l'alliberament de subproductes d'oxidació.
EEM-PARAFAC ha demostrat ser una tècnica econòmica, que no requereix de l'ús de reactius, i ràpida, per a seguir simultàniament l'eliminació de la degradació de fins a 5 FQ fluorescents presents en una mateixa mostra, en presència d'interferències sense calibrar, i obtindre informació sobre les possibles estructures moleculars dels intermediaris de reacció. Els resultats van indicar que la fotòlisi per si sola no és capaç de produir canvis importants en l'estructura de les FQ, mentre que amb (foto-)Fenton, sí que es va observar una notable disminució dels scores dels components PARAFAC associats amb el nucli de FQ. Els assajos de zona d'inhibició que empren E. coli van mostrar que l'activitat antibiòtica va disminuir en paral·lel amb la desintegració de tots els components PARAFAC relacionats amb FQ i subproductes similars a FQ.
L'altre aspecte important de la tesi va ser l'ús de processos Fenton basats en ZVI. Alguns CEC, com els compostos nitroaromàtics, exhibeixen taxes de degradació lentes fins i tot quan són degradats per un AOP. El desenvolupament de trens de tractament basats en ZVI per a la degradació de contaminants ha despertat un gran interés en els últims anys. Aquesta aproximaciót consisteix en un primer pretractament amb ZVI (és a dir, reducció, deshalogenación), seguit del procés Fenton aprofitant els ions de ferro alliberats en el primer pas. Amb la finalitat d'analitzar els possibles avantatges i inconvenients d'aquesta estratègia en les aplicacions de tractament d'aigües residuals, s'han emprat micropartícules de ZVI (mZVI) comercials. Utilitzant àcid p-nitrobenzoic (PNBA) com a contaminant model, es va analitzar l'efecte de la quantitat inicial de mZVI, H2O2, pH, conductivitat, anions i oxigen dissolt. Utilitzant aigua natural en condicions aeròbiques, pH inicial 3,0, i addicionant 1,4 g/L de mZVI, es va aconseguir en 2 h una reducció del 83% de PNBA 6 μM a àcid p-aminobenzoic (PABA). Es va investigar també la conveniència d'eliminar les mZVI després de la fase reductora (abans de l'etapa Fenton) així com la reutilització de les mZVI. El pas de Fenton front el PABA, més reactiu que PNBA, va requerir 50 mg/L de H2O2 per a aconseguir una eliminació de més del 96% en 15 min a pH 7,5 (pH final del pretractament reductiu). Les mZVI reutilitzades van ser efectives almenys amb un cicle complet (reducció/oxidació). Aquest enfocament pot ser interessant per a tractar aigües residuals que contenen contaminants inicialment resistents al HO, però que es redueixen fàcilment, podent disminuir la seua càrrega tòxica i augmentar la seua reactivitat per a un pas d'oxidació posterior. / [EN] Dark Fenton and photo-Fenton were employed to degrade Fluoroquinolones (FQs) (a class of synthetic antibiotics considered CEC) as model pollutants under different conditions: pH (3 - 8), pollutant concentration (3 - 300 μM), number of present FQs (1, 3 and 5), and water matrix (ultra-pure, salty and simulated wastewater). Experiments were performed at bench and pilot plant scales, employing sunlight (simulated and real) and ultraviolet light irradiations. Obtained pollutant abatement rates with Fenton-related processes were compared with photolysis, heterogeneous photocatalysis and H2O2/UV. At equal conditions, only through photo-Fenton process significant FQs mineralization were achieved. In those cases where total organic carbon had not exhibit a considerable decrease, the reason was attributed to the release of oxidation by-products.
Since FQs are fluorescent, we decided to employ fluorescence excitation-emission matrices (EEM) in combination with the chemometric tool, Parallel Factor Analysis (PARAFAC), to track their degradations. Although EEM-PARAFAC related studies are usually focused towards the characterization and monitoring of dissolved organic matter (DOM) in natural waters and wastewater effluents (work also included in this PhD Thesis following the DOM along the different stages of a drinking water plant), it is barely the first time that it is used for the purposes we have here proposed. The objective is demonstrating that EEM-PARAFAC could be a feasible complementary methodology for the study of fluorescent CECs degradations, avoiding the use of expensive and sophisticated techniques (e.g mass spectrometry), not always available.
The other important aspect of the PhD Thesis was the use of ZVI-based Fenton processes. Some CECs such as nitroaromatic compounds, exhibit slow degradation rates even with AOPs. The development of new and more efficient ZVI treatment trains for pollutant degradation has been attracting great interest in the last few years. This approach consists of a first pre-treatment only with ZVI (i.e. reduction, dehalogenation), followed by a Fenton oxidation taking advantage of the released iron ions from the first step. In order to analyse the strategy's plausible advantages and potential drawbacks within wastewater treatment applications, reductive/oxidative treatment train based on commercial ZVI microparticles (mZVI) has been studied. The effect of the initial amount of mZVI, H2O2, pH, conductivity, anions, dissolved oxygen were analysed using p-nitrobenzoic acid (PNBA) as model pollutant. 83% reduction of PNBA 6 μM into p-aminobenzoic acid (PABA) was achieved in natural water at initial pH 3.0 and 1.4 g/L of mZVI under aerobic conditions in 2 h. An evaluation of the convenience of removing mZVI after the reductive phase (before the Fenton oxidation one) was investigated together with mZVI reusability. The Fenton step against the more reactive PABA required 50 mg/L of H2O2 to achieve more than 96% removal in 15 min at pH 7.5 (final pH from the pre-reductive step). At least one complete reuse cycle (reduction/oxidation) was obtained with the separated mZVI. This approach might be interesting to treat wastewater containing pollutants initially resistant to hydroxyl radical (HO), but easily reduced, being able to decrease its toxic load as well as increasing its reactivity for a subsequent oxidation step. / Sciscenko, IM. (2021). Emerging Photochemical Processes Involving Iron for Wastewater Treatment [Tesis doctoral]. Universitat Politècnica de València. https://doi.org/10.4995/Thesis/10251/177357 / TESIS / Compendio
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Occupational exposure to combustion by-products and breast cancer risk in postmenopausal womenPaul-Cole, Kahlila 12 1900 (has links)
Contexte : L’exposition professionnelle aux sous-produits de combustion est répandue et peut contribuer à l'étiologie du cancer du sein. Cette étude vise à estimer l’association entre l’exposition professionnelle à certains sous-produits de combustion et le risque postménopausique de cancer du sein.
Méthodes : Cette étude cas-témoins populationnelle comprenait des femmes ménopausées âgées de 47-75 ans résidant à Montréal, Québec (2008-2011). Les cas incluaient 695 femmes ayant reçu un diagnostic cancer du sein malin et 608 témoins sélectionnés aléatoirement à partir de la Liste électorale du Québec, appariés aux cas en fréquence (groupes d'âge de 5 ans). L’information sur les facteurs de risque et l'historique professionnel a été recueillie par entrevue. Des hygiénistes industriels ont évalué l'exposition à 293 agents, dont six sous-produits de combustion. Le risque de cancer du sein associé à l'exposition professionnelle à certains sous-produits a été estimé, pour l'ensemble des tumeurs et leurs sous-types moléculaires, par régression logistique inconditionnelle avec rapports de cotes ajustés (RC) et intervalles de confiance à 95 % (IC 95%).
Résultats : Des associations positives suggestives ont été trouvées entre l'exposition aux hydrocarbures aromatiques polycycliques et certains sous-types moléculaires de tumeurs : toutes tumeurs, RC=1,18 (IC95%=0,80-1,76), tumeurs luminales A, RC=1,25 (IC95%=0,81-1,93) et tumeurs luminales B, RC=2,09 (IC95%=0,87-4,60). Un risque élevé a été observé avec l'exposition aux fumées de cuisson pour les tumeurs HER2-enrichies (RC=2,63, IC95%=0,98-6,40).
Conclusion : L'exposition à certains sous-produits de combustion peut augmenter le risque de certains sous-types moléculaires de cancer du sein. Des études futures explorant cette association sont justifiées. / Background: Postmenopausal breast cancer is the most common cancer among women, yet little is known about its association with occupational exposures. Exposure to combustion by-products is widespread in occupational settings and may contribute to breast cancer etiology. Here, we sought to estimate the association between lifetime occupational exposure to select combustion by-products and the risk of postmenopausal breast cancer.
Methods: This population-based case-control study included postmenopausal women residing in Montreal, Quebec (2008-2011). Cases comprised 695 women aged 47-75 years diagnosed with incident malignant breast cancer, and 608 controls randomly selected from the Quebec Electoral List, frequency-matched to cases (5-year age groups). Information on risk factors and employment history was collected by interview. Exposure to 293 agents, including six combustion by-products was assessed by industrial hygienists. Unconditional logistic regression was used to estimate adjusted odds ratios (ORs) and 95% confidence intervals (95% CIs) for breast cancer risk, both overall and by tumor molecular subtypes, to occupational exposure to select combustion by-products.
Results: We found suggestive positive associations between exposure to polycyclic aromatic hydrocarbons and certain molecular subtypes of tumors: for all tumors, OR=1.18 (95% CI: 0.80-1.76), Luminal A tumors, OR=1.25 (95% CI: 0.81-1.93) and Luminal B tumors, OR=2.09 (95% CI: 0.87-4.60). Elevated risked were observed for exposure to cooking fumes for HER2-enriched tumors (OR=2.63, 95% CI: 0.98-6.40).
Conclusion: Exposure to select combustion by-products may increase the risk of certain hormonal subtypes of breast cancer. Future studies exploring this association are warranted.
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Caracterización fisicoquímica, tecnológica y funcional del residuo procedente de la obtención de la bebida vegetal de almendra. Estrategias de valorización.Duarte Serna, Stevens 09 October 2024 (has links)
Tesis por compendio / [ES] El mercado de bebidas vegetales está experimentando un crecimiento constante debido a la creciente demanda de productos de origen vegetal. Dentro de este mercado, la bebida de almendra, perteneciente al grupo de las oleaginosas, destaca por su alto contenido en nutrientes, compuestos fenólicos y sus propiedades antioxidantes. Por otra parte, la generación masiva de residuos y subproductos por parte de la industria alimentaria representa uno de los mayores desafíos a nivel global. De acuerdo con la Comisión Europea, aproximadamente se desperdicia un 13% de la producción alimentaria mundial, equivalente a 366 millones de toneladas dentro de la Unión Europea. La industria alimentaria ha estado trabajando en la implementación de los Objetivos de Desarrollo Sostenible (ODS) adoptados por las Naciones Unidas en 2015, con especial atención en el ODS 12, que promueve la producción responsable y sostenible. Este objetivo busca prevenir el desperdicio de alimentos, revalorizar residuos y promover la economía circular como parte de la Agenda 2030.
En este contexto, el objetivo general de la presente tesis fue estudiar las posibilidades de revalorización del subproducto resultante del proceso de obtención de la bebida vegetal de almendra. Determinar las propiedades fisicoquímicas, tecnológicas y funcionales de la materia prima. Evaluar el efecto de la deshidratación (secado con aire caliente y liofilización) sobre las propiedades fisicoquímicas, el contenido de componentes bioactivos, su bioaccesibilidad y su influencia sobre la microbiota. Finalmente, se consideró la posibilidad de obtener un producto deshidratado con probióticos.
La consecución de este objetivo se abordó desde tres enfoques que se presentan en tres capítulos en los que se ha estructurado el apartado de resultados. En el primer capítulo se evaluó el impacto del secado por aire caliente a 60 °C y 70 °C y de la liofilización, sobre las propiedades tecno-funcionales del bagazo de almendra. Se analizaron las curvas de secado y las isotermas de sorción. Luego, se evaluó el efecto del almacenamiento a temperatura ambiente y en condiciones aceleradas de los polvos obtenidos por ambos métodos de secado; durante 6 meses, se monitoreó el crecimiento microbiológico, la acidez, el índice de peróxidos, la capacidad antioxidante y el contenido de polifenoles. Finalmente, se evaluó la idoneidad del polvo de bagazo de almendra como sustituto en la elaboración de productos de panadería, concretamente galletas.
Tanto el secado por aire caliente como la liofilización resultaron ser operaciones adecuadas para estabilizar el bagazo de almendra. Ambos métodos de secado, combinados con un triturado adecuado, proporcionaron polvos con propiedades favorables para su uso en la industria alimentaria. En relación con la actividad antirradical, no se presentaron diferencias significativas entre las muestras deshidratadas, si bien el contenido en fenoles totales fue mayor en las muestras liofilizadas. En cuanto al almacenamiento durante 6 meses, al finalizar dicho periodo se observó un aumento en la capacidad antirradical, así como en el contenido de fenoles totales, especialmente notable en las muestras secadas por aire caliente y sometidas a almacenamiento acelerado. Los valores de acidez e índice de peróxido aumentaron considerablemente durante el almacenamiento acelerado, posiblemente debido a la descomposición de los ácidos grasos. Finalmente, se evaluó la idoneidad del polvo de bagazo de almendra como ingrediente sustitutivo en la elaboración de productos de panadería. Los resultados mostraron la idoneidad del subproducto para ser utilizado como sustituto de la harina de trigo en la elaboración de galletas ya que proporcionó un producto de textura adecuada con mayor contenido en fibra y componentes con capacidad antirradical. / [CA] El mercat de begudes vegetals està experimentant un creixement constant a causa de la demanda creixent de productes d'origen vegetal. Dins aquest mercat, la beguda d'ametlla, pertanyent al grup de les oleaginoses, destaca pel seu alt contingut en nutrients, compostos fenòlics i propietats antioxidants. D'altra banda, la generació massiva de residus i subproductes per part de la indústria alimentària representa un dels desafiaments més grans a nivell global. D'acord amb la Comissió Europea, aproximadament es desaprofita un 13% de la producció alimentària mundial, equivalent a 366 milions de tones dins de la Unió Europea. La indústria alimentària ha estat treballant en la implementació dels Objectius de Desenvolupament Sostenible (ODS) adoptats per les Nacions Unides el 2015, amb especial atenció a l'ODS 12, que promou la producció responsable i sostenible. Aquest objectiu cerca prevenir el malbaratament d'aliments, revalorar residus i promoure l'economia circular com a part de l'Agenda 2030.
En aquest context, l'objectiu general de la present tesi va ser estudiar les possibilitats de revaloració del subproducte resultant del procés d'obtenció de la beguda vegetal d'ametlla. Determinar les propietats fisicoquímiques, tecnològiques i funcionals de la matèria primera. Avaluar l'efecte de la deshidratació (assecat amb aire calent i liofilització) sobre les propietats fisicoquímiques, el contingut de components bioactius, la bioaccessibilitat i la influència sobre la microbiota. Finalment, es va considerar la possibilitat d'obtenir un producte deshidratat amb probiòtics.
La consecució d'aquest objectiu es va abordar des de tres enfocaments que es presenten en tres capítols en el que s'ha estructurat l'apartat de resultats. En el primer capítol es va avaluar l'impacte de l'assecat per aire calent a 60 °C i 70 °C, i de la liofilització, sobre les propietats tecno-funcionals del bagàs d'ametlla. Es van analitzar les corbes d'assecat i les isotermes de sorció. Després, es va avaluar l'efecte de l'emmagatzematge a temperatura ambient i en condicions accelerades de les pols obtingudes pels dos mètodes d'assecat; durant 6 mesos, es va monitoritzar el creixement microbiològic, l'acidesa, l'índex de peròxids, la capacitat antioxidant i el contingut de polifenols. Finalment, es va avaluar la idoneïtat de la pols de bagàs d'ametlla com a substitut en l'elaboració de productes enfornats, concretament galetes.
Tant l'assecat per aire calent com la liofilització van resultar ser operacions adequades per estabilitzar el bagàs d'ametlla. Ambdós mètodes d'assecat, combinats amb un triturat adequat, van proporcionar pols amb propietats favorables per al seu ús a la indústria alimentària. En relació amb l'activitat antirradical, no es van presentar diferències significatives entre les mostres deshidratades, si bé el contingut en fenols totals va ser més gran en les mostres liofilitzades. En relació amb l'emmagatzematge durant 6 mesos, en finalitzar aquest període es va observar un augment en la capacitat antirradical, així com en el contingut de fenols totals, especialment notable a les mostres assecades per aire calent i sotmeses a emmagatzematge accelerat. Els valors d'acidesa i índex de peròxid van augmentar considerablement durant l'emmagatzematge accelerat, possiblement degut a la descomposició dels àcids grassos. Finalment, es va avaluar la idoneïtat de la pols de bagàs d'ametlla com a ingredient substitutiu en l'elaboració de productes enfornats. Els resultats van mostrar la idoneïtat del subproducte per ser utilitzat com a substitut de la farina de blat en l'elaboració de galetes ja que va proporcionar un producte de textura adequada amb més contingut en fibra i components amb capacitat antirradical. / [EN] The vegetable beverage market is experiencing steady growth due to the increasing demand for products of vegetable origin. Within this market, the almond beverage, which belongs to the oilseed group, stands out for its high content of nutrients, phenolic compounds and antioxidant properties. On the other hand, the massive generation of waste and by-products by the food industry represents one of the major global challenges. According to the European Commission, approximately 13% of the world's food production is wasted, equivalent to 366 million tonnes within the European Union. The food industry has been working on the implementation of the Sustainable Development Goals (SDGs) adopted by the United Nations in 2015, with a particular focus on SDG 12, which promotes responsible and sustainable production. This goal aims to prevent food waste, revalue waste and promote the circular economy as part of the 2030 Agenda.
In this context, the general objective of this thesis was to study the possibilities of revaluing the by-product resulting from the process of obtaining almond plant-based beverage. To determine the physicochemical, technological and functional properties of the raw material. Evaluate the effect of dehydration (hot air drying and freeze-drying) on the physicochemical properties, the content of bioactive components, their bioaccessibility and their influence on the microbiota. Finally, the possibility of obtaining a dehydrated product with probiotics was considered.
The achievement of this objective was approached through three perspectives presented in three chapters, structuring the results section accordingly. In the first chapter, the impact of hot air drying at 60 °C and 70 °C and freeze-drying on the techno-functional properties of almond bagasse was evaluated. Drying curves and sorption isotherms were analysed. Then, the effect of storage at room temperature and under accelerated conditions of the obtained powders by both drying methods was evaluated; over a period of 6 months, microbiological growth, acidity, peroxide index, antioxidant capacity, and polyphenol content were monitored. Finally, the suitability of almond bagasse powder as a substitute in the production of bakery products, specifically biscuits, was assessed.
Both hot air drying and freeze drying proved to be suitable operations to stabilise almond bagasse. Both drying methods, combined with appropriate grinding, provided powders with favourable properties for use in the food industry. Regarding the antiradical activity, there were no significant differences between the dehydrated samples, although the total phenol content was higher in the freeze-dried samples. After a 6-month storage period, an increase in antiradical capacity and total phenolic content was observed, particularly noticeable in the samples dried by hot air and subjected to accelerated storage. Acidity and peroxide index values increased considerably during accelerated storage, possibly due to the decomposition of fatty acids. Finally, the suitability of almond bagasse powder as a substitute ingredient in the production of bakery products was evaluated. The results indicated its suitability as a substitute for wheat flour in the production of biscuits, providing a product with appropriate texture, increased fibre content, and components with antiradical capacity. / Duarte Serna, S. (2024). Caracterización fisicoquímica, tecnológica y funcional del residuo procedente de la obtención de la bebida vegetal de almendra. Estrategias de valorización [Tesis doctoral]. Universitat Politècnica de València. https://doi.org/10.4995/Thesis/10251/204146 / Compendio
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Potential of purpose-specific fish feeds for aquaponics and circular multitrophic food production systemsShaw, Christopher 27 May 2024 (has links)
Durch die Nutzung des fischfutterbedingten Nährstoffeintrags für die kombinierte Produktion von Fischen und Pflanzen können Aquaponiksysteme eine nachhaltige Erweiterung von Kreislaufanlagen der Aquakultur (RAS) darstellen. Herkömmliche Aquakulturfutter zielen jedoch auf Fischproduktion mit geringer Umweltbelastung ab und sind somit nicht für die Aquaponik optimiert. Daher weist RAS-Wasser häufig Mängel im Profil gelöster anorganischer Pflanzennährstoffe auf. So war es Ziel dieser Arbeit, die Auswirkungen unterschiedlicher Proteinquellen auf die Nährstoffdynamik in RAS durch Fütterungsversuche mit Afrikanischem Raubwels und Nil-Tilapia zu untersuchen, bei denen Wachstum, gelöste anorganische Nährstoffkonzentrationen im RAS-Wasser und die Ausscheidung von Nährstoffen über den Kot verfolgt wurden. Der Fokus lag auf nachhaltigen alternativen Proteinquellen zu marinem Fischmehl und terrestrischen Pflanzenproteinen: Larvenmehl der Schwarzen Soldatenfliege (BSFM), Welsschlachtabfallmehl (CM), Geflügelschlachtabfallmehl (PM) und Geflügelblutmehl (PBM). Experimentalfutter, die phosphorreiches PM und CM enthielten, förderten erhöhte Ausscheidung von löslichem reaktivem Phosphor, erzeugten die besten gelösten N:P-Verhältnisse im RAS-Wasser verglichen mit einer Hydroponik-Nährlösung und ermöglichten in Kombination mit PBM besseres Wachstum beim Wels als ein vergleichbares kommerzielles Futter. In Futtern basierend auf einer einzigen Proteinquelle führte PM bei Wels und insbesondere bei Tilapia zu ähnlichem Wachstum verglichen mit marinem Fischmehl, wohingegen BSFM und PBM bei beiden Arten Wachstumsleistung beeinträchtigte. Meta-Analysen aller Versuche legen nahe, dass höherer Phosphor-, Kalium- und Magnesiumgehalt im Futter erhöhte Ausscheidung dieser Elemente in gelöster Form bedingt, was sie zu Zielnährstoffen in Aquaponikfuttern macht, während die Optimierung des Protein zu Energie-Verhältnisses im Futter die gelösten N:P- und N:K-Verhältnisse im RAS-Wasser verbessern kann. / By using the nutrient input from fish feeds for the combined production of fish and plants, aquaponic systems can be a sustainable extension of recirculating aquaculture systems (RAS). However, conventional aquaculture feeds are optimized for fish production and reduced environmental impact rather than aquaponics. Hence, RAS water is often characterized by deficiencies regarding its dissolved inorganic plant nutrient profile. Therefore, this thesis aimed to explore the effect of purposeful dietary protein choice on nutrient dynamics in RAS through four systematic feeding trials involving African catfish and Nile tilapia in which growth performance, dissolved inorganic nutrient concentrations in RAS water and solid fecal nutrient excretion were tracked. Focus was on sustainable alternative protein sources to marine fish meal and terrestrial plant proteins: black soldier fly larvae meal (BSFM), catfish by-product meal (CM), poultry by-product meal (PM) and poultry blood meal (PBM). Experimental diets including phosphorus-rich PM and CM supported increased excretion of soluble reactive phosphorus, produced the most favorable dissolved N:P ratios in RAS water when compared to a renowned hydroponic nutrient solution, and, combined with PBM, enabled better growth performance in African catfish than a comparable commercial diet. In single protein source diets, PM produced similar growth performance in African catfish and particularly Nile tilapia versus marine fish meal, whereas BSFM and PBM impaired growth performance in both species. Meta-analyses covering all trials suggest that higher dietary phosphorus, potassium and magnesium content leads to their increased excretion in dissolved form, making them target nutrients for aquaponic feed formulation, while the optimization of the dietary protein to energy ratio can further improve dissolved N:P and N:K ratios in RAS water.
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