To see the other types of publications on this topic, follow the link: Degradation of organic pollutants.
Dissertations / Theses on the topic 'Degradation of organic pollutants'
Create a spot-on reference in APA, MLA, Chicago, Harvard, and other styles
Consult the top 50 dissertations / theses for your research on the topic 'Degradation of organic pollutants.'
Next to every source in the list of references, there is an 'Add to bibliography' button. Press on it, and we will generate automatically the bibliographic reference to the chosen work in the citation style you need: APA, MLA, Harvard, Chicago, Vancouver, etc.
You can also download the full text of the academic publication as pdf and read online its abstract whenever available in the metadata.
Browse dissertations / theses on a wide variety of disciplines and organise your bibliography correctly.
1
Kolář, Michal. "Degradation of organic pollutants employing various photocatalytic systems." Phd thesis, Université Blaise Pascal - Clermont-Ferrand II, 2008. http://tel.archives-ouvertes.fr/tel-00731166.
Full textAbstract:
La dégradation photoinduite du Monuron (herbicide) a été étudiée dans trois systèmes différents produisant des radicaux hydroxyle : en présence du complexe Fe(III)Cit, dans une suspension de TiO2 et dans un système combiné Fe(III)Cit / TiO2. Le but principal était d'améliorer l'efficacité photocatalytique. La spéciation et la photoactivité du complexe ont été déterminées en fonction du pH. La cinétique de dégradation du Monuron photoinduite par le complexe se fait en deux étapes avec deux sources successives de radicaux °OH : 1) photolyse du complexe ; 2) cycle photoredox du fer. La présence de TiO2 améliore l'efficacité du système Fe(III)Cit à pH acide alors qu'à pH neutre l'efficacité du système est complètement inhibée. La concentration en oxygène et le pH sont les facteurs clés en présence du complexe Fe(III)Cit. De plus, dans un système pilote utilisant du TiO2, l'influence d'un solvant organique lors de la dégradation du 4-chlorophénol en milieu aquatique a été examinée.
2
Zaballa, Vicente. "Photoelectrocatalytic degradation of organic pollutants with TiOâ‚‚ electrodes." Thesis, University of Strathclyde, 2001. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.248657.
Full text
3
Kolar, Michal. "Degradation of organic pollutants employing various photocatalytic systems." Clermont-Ferrand 2, 2008. http://www.theses.fr/2008CLF21885.
Full textAbstract:
La dégradation photoinduite du Monuron (herbicide) a été étudiée dans trois systèmes différents produisant des radicaux hydroxyle : en présence du complexe Fe(III)Cit, dans une suspension de TiO2 et dans un système combiné Fe(III)Cit / TiO2. Le but principal était d'améliorer l'efficacité photocatalytique. La spéciation et la photoactivité du complexe ont été déterminées en fonction du pH. La cinétique de dégradation du Monuron photoinduite par le complexe se fait en deux étapes avec deux sources successives de radicaux °OH : 1) photolyse du complexe ; 2) cycle photoredox du fer. La présence de TiO2 améliore l'efficacité du système Fe(III)Cit à pH acide alors qu'à pH neutre l'efficacité du système est complètement inhibée. La concentration en oxygène et le pH sont les facteurs clés en présence du complexe Fe(III)Cit. De plus, dans un système pilote utilisant du TiO2, l'influence d'un solvant organique lors de la dégradation du 4-chlorophénol en milieu aquatique a été examinée
4
Wang, J. "Studies on the degradation of organic pollutants by semiconductor photocatalysis." Thesis, Swansea University, 1999. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.639340.
Full textAbstract:
Over the past decade, many studies have been done on the semiconductor photominieralization of water pollutants. There is still an apparent lack of knowledge or further calcification required concerning details of the photocatalytic degradation mechanism, and factors associated with the reaction. The aim of this thesis is to address various fundamental aspects of semiconductor photocatalysis. Thus in Chapter three, the often used concept that O2 is a necessary reactant in the semiconductor photocatalysis of organic pollutants is challenged in a detailed study of the kinetics of photomineralisation of 4-chlorophenol and acetone, sensitised by TiO2 using metal ions, such as Fe3+, Cu2+ and Hg2+, rather than, and in addition to, O2, as the electron acceptors. Chapter four highlights the poorly understood world of semiconductor photocatalysis kinetics and mechanisms with a study of the effect of light intensity upon the apparent Langmuir-Hinshelwood constants found for the photomineralisation of 4-chlorphenol, sensitised by Degussa P25 powder dispersions. Chapter five describes the results of a detailed study of the kinetics of photomineralisation of 4-CP, sensitised by a film of Degussa P25 - the first example of such a study. The similarities and differences in kinetics of photomineralisation of the dye methylene blue sensitised by TiO2 are explored. This dye features widely in semiconductor photocatalysis as test organic pollutant and is used to evaluate the activities of different photocatalysts. However, the kinetics and underlying mechanisms for photobleaching are much more complex than previously recognised, as revealed by the results of this study.
5
Lam, Shirley. "Effect of sulphate on the anaerobic degradation of organic pollutants (benzoate) /." Hong Kong : University of Hong Kong, 1994. http://sunzi.lib.hku.hk/hkuto/record.jsp?B13813523.
Full text
6
Serrano-Rosales, Benito. "Photo-catalytic degradation of organic water pollutants, energy efficiency and kinetic modeling." Thesis, National Library of Canada = Bibliothèque nationale du Canada, 1998. http://www.collectionscanada.ca/obj/s4/f2/dsk2/tape17/PQDD_0008/NQ31102.pdf.
Full text
7
Hrapovic, L. "Laboratory study of intrinsic degradation of organic pollutants in compacted clayey soil." Thesis, National Library of Canada = Bibliothèque nationale du Canada, 2001. http://www.collectionscanada.ca/obj/s4/f2/dsk3/ftp04/NQ58216.pdf.
Full text
8
Noganta, Siyasanga. "Photocatalytic degradation of organic pollutants using Ag-Fe₃O₄/SiO₂/TiO₂ nanocomposite." Thesis, University of the Western Cape, 2015. http://hdl.handle.net/11394/5208.
Full textAbstract:
>Magister Scientiae - MScThe global lack of clean water for human sanitation and other purposes has become an emerging dilemma for human beings. The presence of organic pollutants in wastewater produced by textile industries, leather manufacturing and chemical industries is an alarming matter for a safe environment and human health. For the last decades, conventional methods have been applied for the purification of water but due to industrialization these methods fall short. Advanced oxidation processes and their reliable application in degradation of many contaminants have been reported as a potential method to reduce and/or alleviate this problem. Lately, it has been assumed that incorporation of some metal nanoparticles such as magnetite nanoparticles as photocatalyst for Fenton reaction could improve the degradation efficiency of contaminants. Core/shell nanoparticles, are extensively studied because of their wide applications in the biomedical, drug delivery, electronics fields and water treatment. The current study is centred on the synthesis of silver-doped Fe₃O₄/SiO₂/TiO₂ photocatalyst. Magnetically separable Fe₃O₄/SiO₂/TiO₂ composite with core–shell structure were synthesized by the deposition of uniform anatase TiO₂ NPs on Fe₃O₄/SiO₂ by using titanium butoxide (TBOT) as titanium source. Then, the silver is doped on TiO₂ layer by hydrothermal method. Integration of magnetic nanoparticles was suggested to avoid the post separation difficulties associated with the powder form of the TiO₂ catalyst, increase of the surface area and adsorption properties. Lastly and most importantly magnetic nanoparticles upsurge the production of hydroxyl groups or reduced charge recombination. The a synthesized catalysts were characterized using Transmission Electron Microscopy, X-ray Diffraction; Infra-red Spectroscopy, Scanning Electron Microscope and Energy Dispersive Spectroscopy. Other characterization techniques includeVibrating Sample Magnetometry, Brunauer Emmett Teller analysis and Thermogravimetric analysis. The average size of the particles size is 72 nm. Furthermore the photocatalytic performances of the magnetic catalysts were assessed in comparison with that commercial titanium dioxide for the degradation of methylene blue using photochemical reactor under ultra violet light. The results showed that the photocatalytic activity was enhanced using Fe₃O₄/SiO₂/TiO₂ and Ag-Fe₃O₄/SiO₂/TiO₂ compared with that for Fe₃O₄, commercial titanium dioxide powder.
9
Sproule, Kenneth. "Microbial production of an aromatic cis-1,2-dihydrodiol and its application in chemical synthesis." Thesis, University of Warwick, 1992. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.334161.
Full text
10
Kurt-Karakus, Perihan Binnur. "Persistent organic pollutants and soils : studies on their distribution, air-soil exchange and degradation." Thesis, Lancaster University, 2006. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.440375.
Full text
11
BALASUBRAMANIAN, GANESH. "EVALUATING THE EFFECT OF SELECTED PROCESS PARAMETERS ON THE PHOTOCATALYTIC DEGRADATION OF ORGANIC POLLUTANTS." University of Cincinnati / OhioLINK, 2002. http://rave.ohiolink.edu/etdc/view?acc_num=ucin1012410668.
Full text
12
Annarapu, Shashidhar. "Thermal Analysis of Binding of Organic Pollutants to Titanium Dioxide." TopSCHOLAR®, 2014. http://digitalcommons.wku.edu/theses/1338.
Full textAbstract:
Conventional waste water treatment processes are not completely effective in removing highly stable organic compounds. Photocatalytic degradation on titanium dioxide is a possible alternative technique for many classes of these compounds. Several studies have been done by other researchers to study mechanisms of photocatalytic degradation, which occurs either through direct oxidation by holes or via indirect oxidation by radical messengers. Titanium dioxide can oxidize substrates directly through hole oxidation mechanisms or indirectly through free radical mechanisms. Substrates must bind onto the catalyst surface to undergo direct oxidation by holes. Thermogravimetric analysis (TGA) was performed on four different classes of compounds; iodinated contrast agents (iohexol and diatrizoate), polycyclic aromatic hydrocarbons (perylene and pyrene), the antibacterial agent triclosan and the pesticide atrazine, to investigate which of the compounds are adsorbed on the surface of titanium dioxide to undergo direct oxidation through electron holes. Differential scanning calorimetry (DSC) was conducted on triclosan and atrazine to determine if the desorption reaction is endothermic or exothermic. Powder X-ray diffraction was performed on all four classes of compounds to observe diffraction pattern of these compounds.
13
Giri, Atanu. "Development of Photocatalysts Supported on Graphitic Carbon Nitride for the Degradation of Organic Water Pollutants." VCU Scholars Compass, 2018. https://scholarscompass.vcu.edu/etd/5692.
Full textAbstract:
Graphitic carbon nitride (g-C3N4) heterojunction composites with the semiconducting metal oxides, CeO2, ZnO and TiO2 are prepared in situ by co-calcination of the precursor materials or by a solvothermal method. The structural, morphological and the optical properties of the prepared materials are studied using various microscopy and spectroscopy techniques. The synthesized composite materials, CeO2/g-C3N4, ZnO/g-C3N4 and TiO2/g-C3N4 are more efficient in the photocatalytic degradation of the water pollutants indigo carmine (IC) and atrazine than the pure metal oxide, g-C3N4, or their physical mixtures. The CeO2/g-C3N4 and ZnO/g-C3N4 composites also exhibit improved degradation efficiencies of atrazine as compared to the individual metal oxide or g-C3N4 materials. The improved photocatalytic activity of the composites are attributed to the effective electron-hole charge separation within composite heterojunction, resulting from the well matched energy levels of the metal oxide and g-C3N4. This strategy could be helpful for the synthesis of other metal oxide and g-C3N4 composites for photocatalytic applications.
14
Law, Cheuk Fung Japhet. "Catalytic advanced oxidation processes for degradation of environmental emerging contaminants." HKBU Institutional Repository, 2019. https://repository.hkbu.edu.hk/etd_oa/610.
Full textAbstract:
In recent years, the increasing release of trace organic chemicals to the aquatic environment have been problematic to both the ecosystem and the human society. These trace organic chemicals, regarded as emerging contaminants, include different categories of chemicals, which are either deemed to be safe for human consumption or they are naturally occurring compounds. As a newly recognized class of emerging contaminant, artificial sweeteners are proven to be one of the most ubiquitous classes of emerging contaminants in environmental waters. Its transformation to different suite of TPs during water treatment processes generated more toxic influence than the parent compound is problematic. The realization of the widespread of emerging contaminants, together with their ambiguous fate and impact to the environment have led to the development of advanced oxidation processes that can effectively attenuate this wide range of contaminants. In this work, several catalytic advanced oxidation processes were studied. On one hand, it aimed to evaluate their effectiveness on the removal of the artificial sweetener - acesulfame; and on the other hand, to shed lights on the future development of catalytic advanced oxidation processes. In the first part of this thesis, the photo-Fenton treatment was evaluated on its potential to effectively remove acesulfame together with the produced transformation products, and the post-treatment toxicity screening. The photo-Fenton treatment was found to be effective in removing both the parent compound and the transformation products, without leading to an increase in toxicity, which is largely related to the effective removal of the transformation products. In attempt to reduce the reliance on UV irradiation, newly synthesized carbon and nitrogen co-doped TiO2-based photocatalyst was applied to capture the simulated sunlight for the degradation of acesulfame. The heterogenous photocatalytic treatment was found to involve several different oxidative reactive species for both degradation and transformation by using several scavengers to alter the degradation profile. Unexpected transformation product was also formed upon treatment in actual water matrix, suggesting the impact of water constituents to the transformation of emerging contaminants. Toxicity results indicated the inability to achieve detoxification, suggesting that a more effective degradation process was needed. To accelerate the degradation process, and enhance the performance at neutral pH, the use of redox mediators for Fenton/Fenton-like system was evaluated. Developed novel Fenton-like system involving copper(II) as transition metal ion, persulfate as oxidant and mercaptosuccinic acid as redox mediator led to effective removal of different contaminants. Elucidation of the proposed oxidation mechanism suggested the role of each components of the system, and the generation of different reactive species for degradation as indicated by the different acesulfame transformation profile obtained. The implementation of redox mediators to Fenton/Fenton-like system was beneficial and an effective approach. In short, this work presents several kinds of catalytic advanced oxidation process and shed lights on improving the degradation performance with directions for the future development of better and more effective water treatment processes.
15
Venegas, Julianna Marie Cebollero. "Photochemistry studies in snow and ice quantification of hydroxyl radicals and degradation of persistent organic pollutants /." Click here for download, 2009. http://proquest.umi.com/pqdweb?did=1827193651&sid=1&Fmt=2&clientId=3260&RQT=309&VName=PQD.
Full text
16
Maloney, Phillip. "Investigation of a Novel Magnesium and Acidified Ethanol System for the Degradation of Persistent Organic Pollutants." Doctoral diss., University of Central Florida, 2013. http://digital.library.ucf.edu/cdm/ref/collection/ETD/id/5987.
Full textAbstract:
For centuries chemists have sought to improve humankind's quality of life and address many of society's most pressing needs through the development of chemical processes and synthesis of new compounds, often with phenomenal results. Unfortunately, there also are many examples where these chemicals have had unintended, detrimental consequences that are not apparent until years or decades after their initial use. There are numerous halogenated molecules in this category that are globally dispersed, resistant to natural degradation processes, bioaccumulative, and toxic to living organisms. Chemicals such as these are classified as persistent organic pollutants (POPs), and due to their negative environmental and health effects, they require safe, effective, and inexpensive means of remediation.
This research focuses on the development and optimization of a reaction matrix capable of reductively dehalogenating several POPs. Initial experiments determined that powdered magnesium and 1% V/V acetic acid in absolute ethanol was the most effective system for degrading polychlorinated biphenyl (PCB), an extraordinarily recalcitrant environmental contaminant. Further studies showed that this matrix also was capable of degrading polychlorinated dibenzo-p-dioxins (PCDDs), polybrominated diphenyl ethers (PBDEs), and four organochlorine pesticides (OCPs); dieldrin, heptachlor, heptachlor epoxide, and chlordane. During this phase of testing, field samples contaminated with chlordane were washed with ethanol and this ethanol/chlordane solution was degraded using the same reaction matrix, thereby demonstrating this technology's potential for “real-world” remediation projects. Finally, a set of experiments designed to provide some insight into the mechanism of dechlorination seems to indicate that two distinct processes are necessary for degradation to occur. First, the passivated outer layer of the magnesium must be removed in order to expose the zero-valent magnesium core. Next, an electron is transferred from the magnesium to the target molecule, causing the cleavage of the halide bond and the subsequent abstraction of either a hydrogen or proton from a solvent molecule. It is anticipated that an understanding of these fundamental chemical processes will allow this system to be tailored to a wide range of complex environmental media.Ph.D.
Doctorate
Chemistry
Sciences
Chemistry
17
Adenuga, Dorcas Oluyemisi. "Facile synthesis of Ag/AgCI/BiOCI composite Z-scheme photocatalyst for visible-light-driven pollutant removal." Diss., University of Pretoria, 2019. http://hdl.handle.net/2263/79177.
Full textAbstract:
Degradation of organic contaminants in wastewaters emanating from industrial processing plants could render the water streams reusable for the purpose of reducing water consumption while protecting the environment from harmful pollutants. Organic pollutants can be removed from water using biological processes that mineralise the organics to H2O and CO2. However, mineralisation by biological processes take a long time and in many cases, total mineralisation is impossible to achieve. Alternatively, organics can be completely degraded and mineralised rapidly using chemical and/or photocatalytic advanced oxidation processes (AOP). Both systems have some short comings. In chemical AOP such as Fenton and photo-Fenton reagents, the chemical agents used remain in the water as pollutants requiring further removal. In photocatalytic oxidation processes, most current technologies use UV light as an energy source. The chemical processes are environmentally incompatible, whereas, the “green” photocatalysis is extremely expensive due to the consumption of electricity by high pressure UV light.
Forerunner investigators of photocatalysis utilised TiO2 as the photocatalyst of choice. It has major drawbacks of which the most important one is that it is only activated under ultraviolet (UV) light irradiation. This high energy consumption made the process practically unfeasible. Solar energy (natural light and heat from sun) has great prospects with regards to acting as a substitute for UV since it is a renewable and cheaper energy source. This work therefore investigated the development of a heterogeneous all-solid-state Z-scheme silver/ silver chloride/ bismuth oxychloride (Ag/AgCl/BiOCl) photocatalyst that is able to utilise natural light through being activated by visible light irradiation. This will successfully serve as a green alternative in the use of renewable energy for pollution reduction while saving energy.
The synthesised photocatalysts were characterised using various techniques. The purity and crystallinity of the synthesised photocatalysts were determined using x-ray diffraction (XRD) while x-ray photoelectron spectroscopy (XPS) was used to determine the elemental composition and chemical states present in the synthesised catalysts as well as confirm the presence of elemental Ag. Fourier-transform infrared spectroscopy (FTIR) specified the functional groups present while the morphology and chemical composition were determined on a scanning electron microscopy (SEM)/ energy dispersive x-ray spectroscopy (EDS). The surface area and pore size were measured on a Brunauer-Emmett-Teller (BET) and thermogravimetric analysis (TGA) was done to determine the thermal degradation of synthesised particles. Ultraviolet-visible spectroscopy (UV-VIS) was done to determine the photoabsorption range and bandgap of the particles as efficiency of photocatalysis is dependent on the properties and morphology of the semiconductor material.
Degradation studies were carried out under both visible and UV light irradiation in a batch reactor. The activity of the synthesised Ag/AgCl/BiOCl photocatalyst was compared to that of commonly used TiO2. Specifically, while 60% degradation was achieved under UV light irradiation by both TiO2 and Ag/AgCl/BiOCl photocatalyst, in visible light irradiation, TiO2 measures only 14% in 4 h while Ag/AgCl/BiOCl measures a photodegradation efficiency of 53%. Other factors such as initial organic contaminants concentration, initial catalyst concentration, pH effects and individual compounds effect were also investigated. The reusability of the catalyst was also reported showing stability of the synthesised catalyst as after a total irradiation time of 48 h, 65% phenol degradation was measured. The phenol degradation kinetics were found to fit the widely used first-order Langmuir-Hinshelwood model. The result from the current study proves the feasibility of a novel process for mineralisation of organic compounds in water under cost effective visible light irradiation for the removal of recalcitrant and refractory organics from water.Dissertation (MEng)--University of Pretoria, 2019.
Chemical Engineering
MEng
Unrestricted
18
Tsai, Hei-lok, and 蔡希樂. "Parametric study on the fabrication and modification of TiO2 nanotube arrays for photoeletrocatalytic degradation of organic pollutants." Thesis, The University of Hong Kong (Pokfulam, Hong Kong), 2010. http://hub.hku.hk/bib/B45160259.
Full text
19
Barbero, Brunella. "Synthesis and in-situ ATR studies of nanostructured titania photocatalysts for the degradation of aqueous organic pollutants." Thesis, Aston University, 2017. http://publications.aston.ac.uk/33428/.
Full textAbstract:
Water is a crucial resource for life but only 3% of global water is fresh and this small amount is ever decreasing due to unwise human activities. Traditional biological treatments require further chemical processing to degrade recalcitrant molecules and the processing of such chemicals necessitates large energy inputs and high costs. Heterogeneous photocatalysis provides a green solution as it harnesses the power of natural sunlight. Titanium dioxide is one of the most extensively studied photocatalysts due to low toxicity, chemical stability and low cost. Despite the powerful intrinsic oxidating ability drawbacks in commercial titania materials stem from the relatively high band gap energy and low surface areas. To overcome this, in this research the aim is to synthesis a novel material which can maximize the efficiency of photocatalytic processes applied to depollution of waste water. Mesoporous silicas with tunable parameters were employed as supports for the anchoring of surface titania species, in order to improve the available active surface area of the catalyst. Highly sophisticated analytical techniques common to the fields of surface science and heterogeneous catalysis were applied to fully characterize the prepared materials and determine structure-function relationships. Screening for the photocatalytic activity of the synthesized materials was performed in jacketed quartz batch reactor irradiated by a UV-vis light source against common organic dyes. Photoactivity of the prepared materials was investigated alongside commercially available titania catalysts to act as benchmarks. In heterogeneous catalysis it is vital to study the interaction between the surface of the catalyst and the probe molecules, including adsorptive and desorptive processes occurring at the solid-liquid interface. ATR-IR spectroscopy was used to investigate this aspect of our reaction, allowing for real time monitoring of reaction kinetics with the use of an innovative flow cell chamber, fit with a quartz window allowing for in-situ UV irradiation.
20
Gangula, Srilatha. "Degradation of Chlorophenols in Swine Waste." TopSCHOLAR®, 2010. http://digitalcommons.wku.edu/theses/151.
Full textAbstract:
Naturally occurring plant derived phenols can be degraded through bacteria in swine waste. Chlorinated phenols, which are not naturally present in the environment, are toxic and generated from industrial activities as such petrochemical, pharmaceutical, plastic, rubber, pesticide, iron, steel, paper production, coal conversion, wood preserving, and cellulose bleaching. Large scale coal gasification and carbonization plants are another source of chlorinated phenols. Although not normally present in the environment, chlorinated phenols are structurally similar to many plant derived phenolics.
It is our hypothesis that bacteria located in swine wastes may also have the ability to degrade chlorinated phenols. Identifying situations (and organisms) in which degradation of pollutants occurs is important field of research.
Experimental work was focused on measuring the degradation of seven chlorinated phenols in swine waste using solid-phase micro-extraction (SPME) and gas chromatography(GC). Microbes in the waste perform respiration or fermentation to obtain the energy they need to carry out their life processes. Fermentation is a process in which electrons are transferred from one organic substrate to another and which results in incomplete degradation of organic compounds. Anaerobic respiration is a process in which organic substrates are degraded completely to CO2, but using substances other than oxygen as the terminal electron acceptor (such as Fe(III), NO3- or SO42-). Anaerobic respiration using these alternative electron acceptors provides an easier pathway for degradation of aromatics than fermentation alone. Usually the abundance of these electron acceptors in waste is low since microbes consume them readily and thus they must be added to the mixture. Our work focused on development of methods for the quantification of chlorinated phenols in swine wastes and results of bioremediation research.
In this study, chlorophenols were extracted by SPME and analysed by GC. This research project mainly focused on the anaerobic degradation of chlorophenols in swine waste. It was observed that the decreased concentration of the chlorophenols was likely due to partitioning of the chlorophenols to solids, sticking to glass bottles and by bacteria present in the swine waste.
In summary, it was observed that by ANOVA and gas production analysis 2,6-dichlorophenol and 2,4,5-trichlorophenol were likely to be degraded by bacteria present in swine waste.
21
Mouele, Emile Salomon Massima. "Degradation of persistent organic pollutants (pharmaceuticals & dyes) by combined dielectric barrier electrohydraulic discharge system and photo catalysts." University of the Western Cape, 2019. http://hdl.handle.net/11394/6976.
Full textAbstract:
Philosophiae Doctor - PhDWater pollution problems have continued to increase not only in South Africa but worldwide due to human activities. The presence of organic toxins and bacteria in water sources is mostly due to population growth, industrial development and agricultural run-off. The accumulation of persistent organic pollutants (POPs) in water and wastewater sources has raised various questions on the safety of potable water used for drinking, households and other activities. Traditional mechanical, biological, physical, and chemical methods such as flocculation, coagulation, reverse osmosis, filtration, ultrafiltration, adsorption and active sludge treatment methods have failed to remove these new xenobiotic from aquatic media. This is due to the fact that instead of degrading the toxins, the methods listed above often transform organic contaminants from one form another. Also, the post treatment of by-products resulting from these methods is costly. In addition, this new generation of contaminants, often referred to as compounds of emerging concern (CECs), exist in tiny concentrations (ng) and conventional techniques have not been designed for these low levels of pollutants which consequently pass through during treatment processes and end up in the treated effluents at minute concentrations (ug/L to ng/L). However, complete remediation of chemical toxins in wastewater treatment plants has not been achieved. A better option involves the direct oxidation of the pollutants in the effluent but so far their complete mineralisation has not been achieved. Advanced oxidation processes (AOPs) have emerged in recent years as adequate techniques for the complete removal of POPs. AOPs focus more on the production of non-selective hydroxyl radicals (OH.) which have been considered as the most powerful oxidants (2.8 V) that directly or indirectly mineralise the organic pollutant into dissolved CO2, H2O and harmless end-products. However, the use of excessive chemicals, corrosion of catalyst supports, wasted UV, ozone escapes and the cost associated with AOPs often limit their application for the removal of POPs from water and wastewater treatment facilities. The principal aim of this study was to optimise a double cylindrical barrier discharge (DBD) system for the removal of low concentration persistent organic pollutants (POPs). The efficiency of the DBD system was initially confirmed by quantification of three main reactive oxygen species including ozone (O3), hydrogen peroxide (H2O2) and hydroxyl radicals (.OH) among others. These three active species were successfully detected and quantified using indigo, per titanyl sulphate and terephthallic acid (TA) spectroscopy methods, respectively. Thereafter, the DBD reactor was optimised by assessing the effect of electrophysico-chemical parameters on the removal efficiencies of two selected pollutants including orange II sodium salt dye (O.II) and sulfamethoxazole (SMX), a pharmaceutical, as model persistent organic pollutants.
2020-09-02
22
Gkaniatsou, Effrosyni. "Elaboration of novel enzymatic immobilization matrices, based on Metal-Organic Frameworks for the catalytic degradation of environmental pollutants." Thesis, Université Paris-Saclay (ComUE), 2019. http://www.theses.fr/2019SACLV005.
Full textAbstract:
Les enzymes sont des biocatalyseurs de plus en plus utilisés pour la transformation de molécules organiques (chimie fine, bioconversions, dépollution, chimie du pétrole) car elles possèdent de très bonnes sélectivité et réactivité, générant rapidement de larges quantités de produit. Cependant, la fragilité des enzymes, notamment en solution, limite souvent leur utilisation. Il est donc crucial de les immobiliser et de les stabiliser dans des supports adaptés. Une grande variété de matrices d’immobilisation (organiques ou inorganiques) a déjà étudiée, mais aucune ne satisfait pleinement aux critères nécessaires pour le développement de bio-réacteurs (accessibilité au site actif de l’enzyme, relargage de l’enzyme, diffusion des réactifs, recyclabilité, stabilité..). En outre, la majorité de ces matrices présente une porosité désordonnée, inadaptée pour une immobilisation homogène. L’utilisation de matériaux hybrides, cristallins et poreux de type Metal-Organic Frameworks (MOFs) a été récemment proposée comme alternative avec des applications en biocatalyse et en biodétection.Le travail de cette thèse a consisté à associer des matériaux de type Metal-Organic Frameworks à une mini-enzyme, la microperoxidase 8 (MP8), afin d’obtenir des matériaux multifonctionnels. Dans une première partie, le MOF mésoporeux, MIL-101(Cr), a été utilisé pour encapsuler la MP8, ce qui a conduit à une amélioration de son activité catalytique dans des conditions qui ne sont pas adéquates pour l’activité enzymatique (conditions acides, forte concentration en H2O2), démontrant ainsi le rôle protecteur du MOF vis-à-vis de l’enzyme. De plus, il a été possible de recycler le biocatalyseur. Cette approche a également permis d’améliorer considérablement la sélectivité de la MP8 pour la dégradation d’un colorant organique toxique négativement chargé, le méthyl orange, grâce à son adsorption sélective par interaction électrostatique avec les particules de MIL-101(Cr). La seconde partie a été consacrée à l’utilisation de matériaux MIL-101(Cr) fonctionnalisés. Tout d’abord, l’influence de la fonctionnalisation du ligand (avec un groupement –NH2 ou –SO3H) sur l’encapsulation de la MP8 ainsi que sur son activité catalytique pour des réactions de sulfoxydation a été étudiée. Il a été montré que l’activité catalytique et la réactivité de la MP8 sont affectées par le microenvironnement spécifique des pores du MOF, notamment pour des réactions de sulfoxydation mettant en jeu des dérivés thioanisole. Ensuite, un MOF à métal mixte (MIL-101(Cr/Fe)) choisi pour ses propriétés catalytiques stables, a été synthétisé et caractérisé. Enfin, la dernière partie de cette thèse a été consacrée à la synthèse in-situ d’un MOF (le microporeux MIL-53(Al)-FA) en présence de biomolécules (BSA) dans des conditions compatibles avec la préservation de la structure protéique (en solution aqueuse à température ambiante). Les matériaux hybrides obtenus ont été caractérisés en couplant de nombreuses techniques. Cette méthode d’encapsulation a conduit à des taux d’immobilisation extrêmement élevés. Une étude préliminaire a été initiée avec l’enzyme, Horseradish Peroxidase , qui conserve son activité catalytique après immobilisationThe use of enzymes in biocatalytic processes has been a challenging goal over the years. While enzymes present exceptional catalytic properties, their fragility hinders their industrial application. Their stabilization and protection are therefore of paramount importance. This can be effectively addressed through their immobilization within host solid matrices. Traditional materials (silica, clays, polymers, biopolymers, porous carbons…) have been widely studied as supports. Their pure organic or inorganic nature often requires a compromise between affinity with enzymes and robustness of the matrix. Besides, most of them have non-ordered porosity, with non-homogenous pore size distributions, unsuitable for homogeneous immobilization. Metal-Organic Frameworks (MOFs) have been recently introduced as alternative supports, thanks to their hybrid nature and their crystalline and highly porous structures.The aim of this PhD was to combine Metal-Organic Frameworks (highly porous and chemically stable polycarboxylate MOFs) and a mini-enzyme, microperoxidase 8 (MP8) to obtain multifunctional biocatalysts. In a first part, the mesoporous MIL-101(Cr) was used as a host matrix to encapsulate MP8. The encapsulation led to an increased catalytic activity under conditions (acidic conditions, high concentration of H2O2) detrimental to the catalytic activity of MP8, thereby demonstrating the protecting effect of MIL-101(Cr) matrix. The biocatalyst was also efficiently recycled. The selectivity of MP8 for the degradation of the harmful negatively charged organic dye methyl orange was also enhanced, thanks to the charged-based selective adsorption of the dye in MIL-101(Cr) porosity. A second part of the work was devoted to the use of functionalized MIL-101(Cr) analogs. First, functionalized ligands (bearing –NH2 and –SO3H groups) were used, and their influence on MP8 encapsulation was evaluated. The catalytic activity toward sulfoxidation reactions was also studied. The successful encapsulation of MP8 was strongly dependent on charge matching between the enzyme and the MOFs particles, while its catalytic activity was affected by the specific microenvironment of the pores. The MOF frameworks also modified the reactivity of MP8 toward different thioanisole derivatives. Then, a mixed metal MOF (MIL-101(Cr/Fe)), selected for its stable catalytic properties, was synthesized and characterized. Finally, the last part was devoted to the in-situ synthesis of MOFs (microporous MIL-53(Al)-FA) in presence of biomolecules (BSA) under compatible conditions with the preservation of the protein’s quaternary structure (aqueous media and room temperature). The resulting hybrid materials were thoroughly characterized and presented high loadings of BSA. A preliminarily study was performed with the enzyme, Horseradish Peroxidase, which retained its catalytic activity after immobilization
23
Eriksson, Johan. "Retention and mobilisation of trinitrotoluene, aniline, nitrobenzene and toluene by soil organic matter /." Umeå : Dept. of Forest Ecology, Swedish Univ. of Agricultural Sciences, 2003. http://epsilon.slu.se/s266.pdf.
Full text
24
Weidemann, Eva. "Waste incineration residues : Persistent organic pollutants in flue gas and fly ash from waste incineration." Doctoral thesis, Umeå universitet, Kemiska institutionen, 2014. http://urn.kb.se/resolve?urn=urn:nbn:se:umu:diva-92765.
Full textAbstract:
Modern societies produce large quantities of municipal solid waste (MSW), which is commonly disposed of by incineration. This has several advantages: it reduces the waste’s volume and sterilizes it while also enabling energy recovery. However, MSW incineration has some notable disadvantages, the most widely debated of which is probably the production and release of persistent organic pollutants (POP) such as polychlorinated dibenzofurans (PCDF), dibenzo-p-dioxins (PCDD), biphenyls (PCB) and naphthalenes (PCN). Of the 210 PCDF and PCDD congeners, 17 are toxic, with hormone-disrupting and carcinogenic properties. Twelve of the 209 PCB congeners and at least 2 of the 75 PCN also exhibit such properties. These POP form in the post-combustion zones of MSW incineration plants and are removed from the flue gas using filtering devices that trap them in the fly ash This thesis concerns the formation and degradation of POP in processes related to MSW incineration. The first paper describes a case study in which PCDD were forming in filters designed to remove them from flue gases, causing emission-related issues in a full-scale MSW incineration plant. It was shown that the PCDD formation was probably due to chlorophenol condensation on the filters’ surfaces. The second paper describes the validation of a cooling probe designed to prevent POP formation during high temperature (>450 °C) flue gas sampling. The results obtained also confirmed that PCDF and PCDD formation takes place at temperatures below 600 °C. In the third paper, three different fly ashes were subjected to thermal treatment under an inert atmosphere in a rotary kiln and in sealed ampoules at 400 °C. The concentrations, degrees of chlorination and congener profiles of the POP in the treated ashes and emitted gases were compared to those for the untreated ashes. The trends observed for PCDF mirrored those for PCN, while the trends for PCDD closely resembled those for PCB. The PCDF congener profiles of the kiln ash were similar regardless of the initial ash composition, suggesting that the mechanisms of PCDF formation were similar in all cases. The fourth paper describes the surface characterization of the three fly ashes studied in paper three by SEM, EDX, XPS and XRD. In addition, the thermal desorption and subsequent degradation of POP from the ashes was studied at temperatures of 300-900 °C. The composition of the gases released as the temperature increased differed between the ashes and depended on their composition. Doping experiments using isotopically labelled PCDF and PCDD suggests that PCDD desorbed at lower temperatures than PCDF. This thesis examines several problems relating to POP formation during MSW incineration, from sampling to the ultimate fate of incineration residues. The results obtained illustrate the wide range of processes that contribute to thermal POP formation and degradation during and after MSW incineration.Förbränning av hushållssopor är en vanlig metod för att hantera ett växande avfallsproblem. Metoden har flera fördelar, såsom minskning av volym och vikt, sterilisering och energiåtervinning. Sopförbränning har dock vissa nackdelar och det mest debatterade är sannolikt utsläpp av persistenta organiska föroreningar (POPs) som polyklorerad dibensofuran (PCDF), dibenso-p-dioxin (PCDD), bifenyl (PCB) och naftalen (PCN). Det finns totalt 210 PCDF- och PCDD- kongener, med mellan ett till åtta klor på kolskelettet, varav 17 är giftiga med hormonstörande och cancerframkallande egenskaper. Även tolv av totalt 209 PCB-kongener samt minst två av totalt 75 PCN-kongener uppvisar liknande egenskaper. Dessa klorerade organiska föroreningar bildas då rökgaserna kyls ner i sopförbränningsanläggningarna och avlägsnas från rökgaserna med hjälp av filter och hamnar i flygaskan. Denna avhandling handlar om bildning och nedbrytning av POPs i sopförbränningsrelaterade processer. Den första artikeln är en fallstudie där PCDD bildas i filtren i en fullskalig sopförbränningsanläggning. Bildningen ledde till förhöjda halter organiska föroreningar i rökgaserna, vilket ledde till ökade utsläpp. Den funna bildningsvägen för PCDD i filtren befanns sannolikt bero på kondensation av klorfenoler på filterytorna. Den andra artikeln är en valideringsstudie av en kylprob avsedd att användas vid rökgasprovtagning vid hög temperatur (> 450 °C) för att undvika bildning av POPs under provtagningen. Studien bekräftade att majoriteten av PCDF- och PCDD- bildning i rökgaser från sopförbränning sker vid temperaturer under 600 °C. I den tredje artikeln berättas om behandling av tre olika flygaskor från olika sopförbränningsanläggningar. Askorna behandlades vid 400 °C i inert atmosfär i både en roterugn och i förseglade ampuller. De resulterande koncentrationerna, kloreringsgraderna och kongenprofilerna av de organiska föroreningarna jämfördes. Likheter hittades mellan PCDF och PCN, medan PCDD och PCB betedde sig på ett annat sätt. Studien fann också att PCDF kongenprofiler i aska som behandlats i roterugnen liknade varandra, oberoende av askornas sammansättning, vilket tyder på en liknande bildningsväg. För den fjärde artikeln, genomfördes ytkarakterisering (SEM, EDX, XPS och XRD) på de tre flygaskorna från artikel tre som sedan hettades upp från 30 °C till 900 °C i vacuum. Det som frigjordes på grund av uppvärmningen samt nedbrytningsprodukter från askorna studerades med hjälp av masspektrometri och infraröd spektroskopi. Studien fann att de gaser som frigjordes när temperaturen ökade skilde mellan askorna, beroende på deras sammansättning. Studien fann också att när aska dopad med isotopmärkt PCDF och PCDD utsattes för samma behandling, frigjordes PCDD vid lägre temperatur än PCDF. Denna avhandling berör flera aspekter av problematiken kring klorerade organiska föroreningar som bildas vid sopförbränning, från provtagning till hur man ska hantera flygaskan. Avhandlingen belyser även olika typer av bildning och nedbrytning av POPs i varma processer kopplade till sopförbränning.
25
Schenker, Urs Walter. "The role of intermediate degradation products for the assessment of persistent organic pollutants in a global multi-media-model /." Zürich : ETH, 2008. http://e-collection.ethbib.ethz.ch/show?type=diss&nr=17750.
Full text
26
Yip, Chi Kin. "Novel clay-based metal composites as applicable heterogeneous catalysts for the photo-assisted degradation of textile organic pollutants in water /." View abstract or full-text, 2005. http://library.ust.hk/cgi/db/thesis.pl?EVNG%202005%20YIP.
Full text
27
Mbiri, Anne Wanjira [Verfasser], Michael [Akademischer Betreuer] Wark, and Frank [Akademischer Betreuer] Rößner. "Photocatalytic degradation of selected organic pollutants in water on zirconium modified TiO2 photocatalyst / Anne Wanjira Mbiri ; Michael Wark, Frank Rößner." Oldenburg : BIS der Universität Oldenburg, 2018. http://d-nb.info/1175091642/34.
Full text
28
Afsarmanesh, Tehrani Rouzbeh. "AEROBIC BACTERIAL DEGRADATION OF HYDROXYLATED PCBs: POTENTIAL IMPLICATIONS FOR NATURAL ATTENUATION OF PCBs." Diss., Temple University Libraries, 2013. http://cdm16002.contentdm.oclc.org/cdm/ref/collection/p245801coll10/id/216532.
Full textAbstract:
Civil EngineeringPh.D.
Polychlorinated biphenyls (PCBs) are toxic and persistent chemicals that have been largely dispersed into the environment. The biological and abiotic transformations of PCBs often generate hydroxylated derivatives, which have been detected in a variety of environmental samples, including animal tissues and feces, water, and sediments. Because of their toxicity and widespread dispersion in the environment, hydroxylated PCBs (OH-PCBs) are today increasingly considered as a new class of environmental contaminants. Although PCBs are known to be susceptible to microbial degradation under both aerobic and anaerobic conditions, bacterial degradation of OH-PCBs has received little attention. The overall objective of this study is therefore to evaluate the transformation of mono-hydroxylated PCBs by the well characterized aerobic PCB-degrading bacterium, Burkholderia xenovorans LB400. In order to achieve our overall objective, a series of model mono-hydroxylated PCBs have been selected and they are used to determine the toxicity of hydroxylated congeners toward the bacterium B. xenovorans LB400. The biodegradation kinetics and metabolic pathways of the selected OH-PCBs by B. xenovorans LB400 are then characterized using GC/MS. To understand further the molecular basis of the metabolism of OH-PCBs by B. xenovorans LB400, gene expression analyses are conducted using reverse-transcription real-time (quantitative) polymerase chain reaction (RT-qPCR) and microarray technology. More formally, the specific aims of the proposed research are stated as follows: (1) To evaluate the toxicity of selected mono-hydroxylated derivatives of lesser-chlorinated PCBs toward the bacterium B. xenovorans LB400. (2) To assess the degradation of the selected OH-PCBs by B. xenovorans LB400. (3) To gain further understanding of the molecular bases of the metabolism of the selected OH-PCBs by B. xenovorans LB400. Three hydroxylated derivatives of 4-chlorobiphenyl and 2,5-dichlorobiphenyl, including 2'-hydroxy-, 3'-hydroxy-, and 4'-hydroxy- congeners, were significantly transformed by Burkholderia xenovorans LB400 when the bacterium was growing on biphenyl (biphenyl pathway-inducing conditions). On the contrary, only 2'-OH-4-chlorobiphenyl and 2'-OH-2,5-dichlorobiphenyl were transformed by the bacterium growing on succinate (conditions non-inductive of the biphenyl pathway). Gene expression analyses showed that only exposure to 2'-OH-4-chlorobiphenyl and 2'-OH-2,5-dichlorobiphneyl resulted in induction of key genes of the biphenyl pathway, when cells grown on succinate. These observations suggest that 2'OH-PCBs were capable of inducing the genes of biphenyl pathway. These results provide the first evidence that bacteria are able to cometabolize PCB derivatives hydroxylated on the non-chlorinated ring. Genome-wide transcriptional analyses using microarrays showed that 134 genes were differentially expressed in cells exposed to biphenyl, 2,5-dichlorobiphenyl, and 2'-OH-2,5-dichlorobiphneyl as compared to non-exposed cells. A significant proportion of differentially expressed genes were simultaneously expressed or down regulated by exposure to the three target compounds i.e., biphenyl, 2,5-DCB, and 2'-OH-2,5-DCB, which suggests that these structurally similar compounds induce similar transcriptional response of B.xenovorans LB400. Results of this study may have important implications for the natural attenuation of PCBs and fate of OH-PCBs in the environment. The recalcitrance to biodegradation and the high toxicity of some OH-PCBs may provide a partial explanation for the persistence of PCBs in the environment.
Temple University--Theses
29
Wang, Jing. "Development of Graphitic Carbon Nitride based Semiconductor Photocatalysts for Organic Pollutant Degradation." Doctoral thesis, KTH, Tillämpad processmetallurgi, 2015. http://urn.kb.se/resolve?urn=urn:nbn:se:kth:diva-173216.
Full textAbstract:
As a potential solution to the global energy and environmental pollution, design and synthesis of artificial photocatalysts with high activities have attracted increasing scientific interests worldwide. In recent years, the graphitic carbon nitride (g-C3N4) has shown new possible applications in the photocatalytic field due to its unique properties. However, the photocatalytic efficiency of the pristine g-C3N4 is greatly limited by the high recombination rate of the photo-induced electron-hole pairs. In this thesis, the aim is to design and fabricate efficient g-C3N4 based photocatalysts with enhanced photocatalytic activities under a visible light irradiation. In order to achieve this goal, two strategies have been employed in the present thesis. First, the as-obtained g-C3N4 was used as the host material to construct staggered-aligned composite photocatalysts by selecting semiconductors with suitable band positions. By this method, three kinds of g-C3N4-based composite photocatalysts such as g-C3N4/ZnS nanocage, g-C3N4/m-Ag2Mo2O7 and g-C3N4/MIL-88A were successfully fabricated. Second, the microstructure of the g-C3N4 was modified by the H2O2-treatment at an elevated temperature and ambient pressure. In this study, the g-C3N4 was prepared by a simple pyrolysis of urea. As for all the as-synthesized phtocatalysts, the structures, morphologies and the optical properties were carefully characterized by the following techniques: XRD, SEM, TEM, FT-IR and DRS. Also, the band edge positions of m-Ag2Mo2O7 and MIL-88A were studied by the Mott-Schottky methods. Thereafter, the photocatalytic activities were evaluated by using a solution of rhodamine B (RhB) as a target pollutant for the photodegradation experiments performed under a visible light irradiation. The results showed that all the aforementioned g-C3N4-based photocatalysts exhibited enhanced photocatalytic activities in comparison with the pristine g-C3N4. For the case of the g-C3N4-based composite photocatalysts, the enhancement factor over the pristine g-C3N4 can achieve values ranging from 2.6 to 3.4. As for the H2O2-treated g-C3N4, the degradation rate constant can be 4.6 times higher than that of the pristine g-C3N4. To understand the key factors in new materials design, we also devote a lot of efforts to elucidate the basic mechanisms during the photocatalytic degradation of organic pollutant. Based on the results of the active species trapping (AST) experiments, the main active species in each photocatalytic system were determined. In the g-C3N4/m-Ag2Mo2O7 and the g-C3N4/MIL-88A system, three kinds of active species of ·O2-, h+ and ·OH were found to be involved in the photocatalytic reaction. Among them, the ·O2- and h+ were the main active species. In the g-C3N4/ZnS and H2O2-treated g-C3N4 photocatalytic systems, the main active species was determined as the ·O2-. The reaction pathways of these active species were also demonstrated by comparing the band edge positions with the potentials of the redox couple. In addition, the relationship between the active species and the photocatalytic behaviors of N-de-ethylation and conjugated structure cleavage were studied. Finally, possible mechanisms to explain the enhanced photocatalytic activities were proposed for each photocatalytic system. The results in this thesis clearly confirm that the photocatalytic activity of the g-C3N4 based photocatalyst can efficiently be enhanced by constructions of staggered-aligned composites and by modification of the microstructure of the g-C3N4. The enhanced photocatalytic performance can mainly be ascribed to the efficient separation of the photo-induced electron-hole pairs and the increase of the active sites for the photocatalytic reaction.QC 20150909
30
Ren, Meijie [Verfasser], and F. H. [Akademischer Betreuer] Frimmel. "TiO2: Application in Photocatalysis for the Degradation of Organic Pollutants and Aggregation Behavior in Aquatic Systems / Meijie Ren. Betreuer: F. H. Frimmel." Karlsruhe : KIT-Bibliothek, 2015. http://d-nb.info/1073937518/34.
Full text
31
Wiegert, Charline. "Application of two dimensional compound specific carbon-chlorine isotope analyses for degradation monitoring and assessment of organic pollutants in contaminated soil and groundwater." Doctoral thesis, Stockholms universitet, Institutionen för tillämpad miljövetenskap (ITM), 2013. http://urn.kb.se/resolve?urn=urn:nbn:se:su:diva-93923.
Full textAbstract:
Nearly 250,000 sites with past and present potentially polluting activities need urgent remediation within Europe. Major pollutants include organochlorines (OCls), e.g. chlorinated ethenes (CEs) and hexachlorocyclohexanes (HCHs), mainly used as industrial solvents and pesticides, respectively. Due to improper handling and disposal, OCls contaminants are present in the soil or groundwater surrounding sites, where they have been produced or used. CEs and HCHs can undergo degradation by microorganisms indigenous to the soil or groundwater. Therefore natural attenuation (NA), relying on the in situ biodegradation of pollutants, is considered as a cost effective remediation strategy, yet it requires accurate monitoring methods. Compound specific isotope analysis (CSIA) is a powerful tool to provide information on the extent of degradation and, when combining two isotope systems (2D-CSIA), such as carbon (δ13C) and chlorine (δ37Cl), on reaction mechanisms. The diagnostic reaction-specific isotope enrichment factors (εC and εCl) were determined in laboratory experiments for the anaerobic degradation of PCE, TCE (Paper II) and α-HCH (Paper III) by mixed bacterial cultures enriched from CEs and HCHs contaminated sites, respectively. The related mechanism-specific εCl/εC ratios were calculated as 0.35 ± 0.11 (PCE), 0.37 ± 0.11 (TCE) and 0.52 ± 0.23 (α-HCH). These values are smaller than previously reported values for pure cultures. This is explained by the microbial community composition changes observed during degradation of PCE and α-HCH, which also reflect the variability of the microbial community at the field level. Furthermore, εCl/εC ratio might be bacteria specific. These values allowed the estimation of the extent of contaminant degradation at the respective study sites (Paper III and IV). Application of both isotope systems (δ13C and δ37Cl) led to comparable estimates. However the choice of representative ε values is crucial for an accurate assessment. These studies show that CSIA is useful to quantify in situ degradation of OCls contaminants and identify reaction pathways, by combining δ13C and δ37Cl.At the time of the doctoral defense, the following papers were unpublished and had a status as follows: Paper 3: Submitted. Paper 4: Manuscript.
32
Mezughi, Khaled M. "Heterogeneous photocatalytic degradation of organic pollutants in water over nanoscale powdered titanium dioxide. The photocatalytic degradation of organic compounds in water (Reactive Orange 16, Triclocarbon, Clopyralid and Estrogens (estrone, 17ß-estradiol, and 17α-ethinylestradiol)) was studied; the reaction kinetics and the effect of the operating parameters on the performance of the system were determined; a comparison with other advanced oxidation processes (O3, H2O2, UV) was also made." Thesis, University of Bradford, 2010. http://hdl.handle.net/10454/4865.
Full textAbstract:
Organic contaminants from industrial and/or domestic effluents may be harmful to humans directly or indirectly by degrading the quality of the aquatic environment. Consequently these contaminants must be reduced to levels that are not harmful to humans and the environment before disposal. Chemical, physical and biological methods exist for the removal of these pollutants from effluents. Among the available chemical methods, heterogeneous photocatalytic oxidation has been found particularly effective in removing a large number of persistent organics in water. In this study, photocatalytic degradation was explored for the removal of reactive azo-dye (textile dye), triclocarban (disinfectant), clopyralid (herbicide) and three endocrine disrupting compounds (EDCs) (estrone, 17ß-estradiol and 17α-ethinylestradiol) from synthetic effluents. The major factors affecting the photocatalytic processes including the initial concentration of the target compounds, the amount of catalyst, the light intensity, the type of catalyst, the electron acceptor, the irradiation time and the pH were studied. Other oxidation techniques including (O3, H2O2, UV) were also studied.
Generally UV light is used in combination with titanium dioxide, as photocatalyst, to generate photoinduced charge separation leading to the creation of electron-hole pairs. The holes act as electron acceptors hence the oxidation of organics occur at these sites. These holes can also lead to the formation of hydroxyl radicals which are also effective oxidants capable of degrading the organics.
The results obtained in this study indicated that photolysis (i.e. UV only) was found to have no effect on the degradation of reactive azo-dye (RO16). However, complete photocatalytic degradation of 20 mg/L (3.24×10-2 mM) RO16 was achieved in 20 minutes in the presence of 1g/L TiO2 Degussa P25 at pH 5.5. Comparison between various types of catalysts (i.e. Degussa P25, VP Aeroperl, Hombifine N) gave varied results but Degussa P25 was the most effective photocatalyst hence it was selected for this study. For RO16 the optimum catalyst concentration was 0.5 g/L TiO2 with initial concentration of 20 mg/L RO16. It was found that the disappearance of RO16 satisfactorily followed the pseudo first-order kinetics according to Langmuir-Hinshelwood (L-H) model. The rate constant was k= 0.0928 mol/min. Photodegradation of TCC was studied in 70%v acetonitrile: 30%v water solutions. UV light degraded TCC effectively and the reaction rates increased with decreasing initial concentration of TCC. UV/TiO2 gave unsatisfactory degradation of triclocarban (TCC) since only 36% were removed in 60 minutes with initial concentration of TCC 20 mg/L. The degradation of clopyralid and the EDCs was studied using three oxidation systems UV/TiO2, UV/H2O2 and O3. Complete degradation of clopyralid (3,6-DCP) was achieved with UV/TiO2 in about 90 minutes at an optimum catalyst concentration of 1g/L. Zero-order kinetics was found to describe the first stage of the photocatalytic reaction in the concentration range 0.078-0.521 mM. At pH 5 the rate constant was 2.09×10-6-4.32×10-7 M.s-1.Complete degradation of all the three EDCs was achieved with UV/H2O2 in 60 minutes at catalyst concentration of (2.94×10-2 M). On the other hand complete degradation of the EDCs was achieved in just 2 minutes with ozonation. For high concentration EDCs, TiO2/UV gave low efficiency of degradation as compared with ozone and H2O2/UV. First-order kinetics was found to describe the photocatalytic reaction of the EDCs.Education Service Department of the Libyan Government
33
Mezughi, Khaled M. "Heterogeneous photocatalytic degradation of organic pollutants in water over nanoscale powdered titanium dioxide : the photocatalytic degradation of organic compounds in water (Reactive Orange 16, Triclocarbon, Clopyralid and Estrogens (estrone, 17ß-estradiol, and 17α-ethinylestradiol)) was studied : the reaction kinetics and the effect of the operating parameters on the performance of the system were determined; a comparison with other advanced oxidation processes (O₃, H₂O₂, UV) was also made." Thesis, University of Bradford, 2010. http://hdl.handle.net/10454/4865.
Full textAbstract:
Organic contaminants from industrial and/or domestic effluents may be harmful to humans directly or indirectly by degrading the quality of the aquatic environment. Consequently these contaminants must be reduced to levels that are not harmful to humans and the environment before disposal. Chemical, physical and biological methods exist for the removal of these pollutants from effluents. Among the available chemical methods, heterogeneous photocatalytic oxidation has been found particularly effective in removing a large number of persistent organics in water. In this study, photocatalytic degradation was explored for the removal of reactive azo-dye (textile dye), triclocarban (disinfectant), clopyralid (herbicide) and three endocrine disrupting compounds (EDCs) (estrone, 17ß-estradiol and 17α-ethinylestradiol) from synthetic effluents. The major factors affecting the photocatalytic processes including the initial concentration of the target compounds, the amount of catalyst, the light intensity, the type of catalyst, the electron acceptor, the irradiation time and the pH were studied. Other oxidation techniques including (O3, H2O2, UV) were also studied. Generally UV light is used in combination with titanium dioxide, as photocatalyst, to generate photoinduced charge separation leading to the creation of electron-hole pairs. The holes act as electron acceptors hence the oxidation of organics occur at these sites. These holes can also lead to the formation of hydroxyl radicals which are also effective oxidants capable of degrading the organics. The results obtained in this study indicated that photolysis (i.e. UV only) was found to have no effect on the degradation of reactive azo-dye (RO16). However, complete photocatalytic degradation of 20 mg/L (3.24×10-2 mM) RO16 was achieved in 20 minutes in the presence of 1g/L TiO2 Degussa P25 at pH 5.5. Comparison between various types of catalysts (i.e. Degussa P25, VP Aeroperl, Hombifine N) gave varied results but Degussa P25 was the most effective photocatalyst hence it was selected for this study. For RO16 the optimum catalyst concentration was 0.5 g/L TiO2 with initial concentration of 20 mg/L RO16. It was found that the disappearance of RO16 satisfactorily followed the pseudo first-order kinetics according to Langmuir-Hinshelwood (L-H) model. The rate constant was k= 0.0928 mol/min. Photodegradation of TCC was studied in 70%v acetonitrile: 30%v water solutions. UV light degraded TCC effectively and the reaction rates increased with decreasing initial concentration of TCC. UV/TiO2 gave unsatisfactory degradation of triclocarban (TCC) since only 36% were removed in 60 minutes with initial concentration of TCC 20 mg/L. The degradation of clopyralid and the EDCs was studied using three oxidation systems UV/TiO2, UV/H2O2 and O3. Complete degradation of clopyralid (3,6-DCP) was achieved with UV/TiO2 in about 90 minutes at an optimum catalyst concentration of 1g/L. Zero-order kinetics was found to describe the first stage of the photocatalytic reaction in the concentration range 0.078-0.521 mM. At pH 5 the rate constant was 2.09×10⁻⁶ ± 4.32×10⁻⁷ M.s⁻¹. Complete degradation of all the three EDCs was achieved with UV/H₂O₂ in 60 minutes at catalyst concentration of (2.94×10⁻² M). On the other hand complete degradation of the EDCs was achieved in just 2 minutes with ozonation. For high concentration EDCs, TiO₂/UV gave low efficiency of degradation as compared with ozone and H2O2/UV. First-order kinetics was found to describe the photocatalytic reaction of the EDCs.
34
Fernández, Fernández Lucia. "Degradation of 17β-estradiol in water media by photosensitized and biodegradation processes." Doctoral thesis, Universidade de Aveiro, 2017. http://hdl.handle.net/10773/22453.
Full textAbstract:
Doutoramento em QuímicaNovos métodos de tratamento de água são requeridos como um resultado a partir da crescente sensibilização para a redução do impacto da poluição no ambiente. As principais vias para a destruição de compostos tóxicos em água são os processos de biodegradação e fotodegradação. A degradação biológica de um composto químico refere-se à eliminação do poluente pela actividade metabólica de microrganismos. A fotodegradação é um mecanismo eficiente para degradar simultaneamente diferentes tipos de compostos orgânicos. No entanto, a fotodegradação pode implicar custos elevados relacionados com a produção dos fotocatalisadores e o consumo energético. Na perspectiva de abordagens sustentáveis para o tratamento da água, sugere-se a combinação de tratamentos de fotodegradação e biológicos. Os compostos disruptores endócrinos (CDEs) são considerados pela investigação como uma prioridade elevada, pois são uma fonte de potencial adverso para efeitos de saúde ecológica nas águas ambientais. O 17β-estradiol (E2), um recalcitrante CDE, foi seleccionado como poluente alvo neste trabalho. Nesta dissertação descreve-se a preparação e a avaliação fotocatalítica de novos materiais híbridos à base de nanopartículas de magnetita decoradas com porfirinas ou ftalocianinas. Este estudo apresenta a aplicação destes fotocatalisadores em modos batch e de fluxo, bem como a sua utilização em águas residuais reais para remoção de diferentes poluentes orgânicos. Adicionalmente, modificações ligeiras destes materiais permitem a sua utilização como agentes antimicrobianos para fins de desinfecção da água contra bactérias patogénicas. O rastreio de estirpes bacterianas capazes de metabolizar o E2 como poluente orgânico alvo em águas provocou a descoberta de utilizações relevantes da estirpe bacteriana Bacillus licheniformis, isolada previamente a partir de sedimentos de profundidade do mar no Golfo de Cádiz. Bacillus licheniformis apresenta uma grande versatilidade em aplicações de remediação de água, sendo capaz de remover diferentes estrogênios em concentrações relevantes (ng·L-1) em águas residuais. Finalmente, o estudo de uma abordagem combinada para o tratamento de águas foi focado na capacidade de Bacillus licheniformis para tratar a água, a partir da qual foi previamente e parcialmente foto-tratada pela ação de um material híbrido, sob irradiação de luz branca.
New methods for water treatment are required as a result from an increasing awareness in the reduction of the pollution impact in the environment. The main routes for destroying toxic compounds in water are biodegradation and photodegradation processes. Biological degradation of a chemical refers to the elimination of the pollutant by the metabolic activity of microorganisms. Photodegradation is an efficient mechanism for simultaneously degrade different types of organic compounds. However, photodegradation may imply high costs related to the photocatalysts’ production and energetic consumption. In the perspective of sustainable approaches for water treatment, the combination of photo- and biological treatments are proposed. Endocrine disrupting compounds (EDCs) are considered as high research priority being a source of potential adverse ecological health effects in environmental waters. 17β-estradiol (E2), a recalcitrant EDC, was selected as target pollutant in this work. In this dissertation, the preparation and photocatalytic evaluation of new hybrid materials based on magnetite nanoparticles decorated with porphyrins or phthalocyanines are described. This study presents the application of these photocatalysts in both batch and flow modes, as well as their use in real wastewaters for the removal of different organic pollutants. In addition, slight modifications of these materials allow their utilization as antimicrobial agents for water disinfection purposes, against pathogenic bacteria. The screening of bacterial strains able to metabolize E2 as target organic pollutant in water caused the finding of relevant uses of the bacterial strain Bacillus licheniformis, previously isolated from deep sea sediments in the Gulf of Cádiz. Bacillus licheniformis displays great versatility in water remediation applications, being able to remove different estrogens in relevant concentrations (ng·L-1) in wastewaters. Finally, the study of a combined approach for water treatment was focused on the ability of Bacillus licheniformis to treat water, which previously was partially photo-treated by the action of a hybrid material, under white light irradiation.
35
Zhou, Ming. "Novel photocatalytic TiO2-based porous membranes prepared by plasma-enhanced chemical vapor deposition (PECVD) for organic pollutant degradation in water." Thesis, Montpellier, 2015. http://www.theses.fr/2015MONTS090/document.
Full textAbstract:
Le dépôt chimique en phase vapeur assisté par plasma est appliqué pour préparer des couches minces amorphes de TiO2 à basse température. Un recuit à 300 °C pendant un temps minimum de 4,5 h permet de former la phase cristalline anatase. Les principales caractéristiques de ces couches minces comme leur structure cristalline, leur microstructure, leur largeur de bande interdite et leur hydrophilie de surface, sont déterminées. Leurs performances fonctionnelles comme photocatalyseurs sont d'abord examinées selon le test breveté par Pilkington, consistant à éliminer sous irradiation UV de l'acide stéarique préalablement adsorbé sur les couches de TiO2 ici déposées sur des plaquettes de silicium. Des membranes M100 (couche continue de TiO2) et M800 (couche de TiO2 couvrant les grains de support) sont préparées sur les couches de surface macroporeuses de supports poreux en alumine, de tailles moyennes de pores respectives, 100 nm et 800 nm. Ces membranes sont testées en condition "statique", avec la diffusion d'un soluté organique dilué dans l'eau. Pour le bleu de méthylène, on montre que la quantité de composé détruit par unité de surface de membrane et par unité de temps est égale à 2 × 10-8 mol m-2 s-1 pour la membrane M100 et 1 × 10-8 mol m-2 s- 1 pour la membrane M800. Ces membranes sont également testées dans des conditions "dynamiques", à savoir en procédé baromembranaire, avec deux configurations différentes (couche photocatalytique du côté de l'alimentation ou du côté du perméat) et trois composés organiques différents (bleu de méthylène, acide orange 7 et phénol). La modélisation du procédé (adsorption et réaction photocatalytique) est finalement réalisée à partir des données expérimentales disponiblesPlasma-enhanced chemical vapor deposition is applied to prepare amorphous TiO2 thin films at low temperature. Post-annealing at 300 °C for minimal staying time 4.5 h is required to form crystalline anatase phase. Characteristics of the TiO2 thin films including crystalline structure, microstructure, band gap and surface hydrophilicity, are determined. Functional performance of these anatase thin films as photocatalysts is first examined with patented Pilkington assessment by removing, under UV irradiation, stearic acid initially adsorbed on TiO2 layers here deposited on silicon wafers. Membranes M100 (TiO2 continuous layer) and M800 (TiO2-skin on support grain) are prepared on the macroporous top layer of porous alumina supports with an average pore size of 100 nm and 800 nm, respectively. These membranes are tested in “static” condition under the effect of diffusion of an organic solute in water. For Methylene Blue it is shown that the quantity of destroyed compound per unit of membrane surface area and per unit of time is equal to 2×10−8 mol m-2 s-1 for M100 and 1×10−8 mol m-2 s-1 for M800. These membranes are also tested in “dynamic” conditions, i.e. pressure-driven membrane processes, with two different configurations (photocatalytic layer on the feed side or on the permeate side) and three different organics (Methylene Blue, Acid Orange 7 and phenol). Process modelling (adsorption and photocatalysis reaction) is finally carried out from the available experimental outputs
36
Mai, Trang. "FUNCTIONALIZATION OF IRON OXIDE NANOPARTICLES AND THE IMPACT ON SURFACE REACTIVE OXYGEN SPECIES GENERATION FOR POTENTIAL BIOMEDICAL AND ENVIRONMENTAL APPLICATIONS." UKnowledge, 2019. https://uknowledge.uky.edu/cme_etds/102.
Full textAbstract:
Iron oxide nanoparticles (IONPs) have been widely studied for a variety of applications, from biomedical applications (e.g., cell separation, drug delivery, contrast agent for magnetic resonance imaging and magnetically mediated energy delivery for cancer treatment) to environmental remediations (e.g., heavy metal removal and organic pollutants degradation). It has been demonstrated that IONPs can induce the production of reactive oxygen species (ROS) via Fenton/Haber-Weiss reactions which has been shown to be one of the key underlying mechanisms of nanoparticles toxicity. This inherent toxicity of nanoparticles has been shown to enhance the efficacy of traditional cancer therapies such as chemotherapy and radiation. In addition, the generation of ROS induced by IONPs has been also studied as advanced oxidation processes (AOP) for wastewater treatment. Recent research has also shown that exposure to an alternating magnetic field can significantly enhance the generation of ROS induced by IONPs. Moreover, the coatings of IONPs play an important role on the surface reactivity of nanoparticles since it can prevent the generation of ROS via Fenton chemistries at the surface of the nanoparticles.
In this work, co-precipitated IONPs were functionalized with small molecules including citric acid, sodium phosphate, amino silane and dopamine. The impact of coating on surface reactivity of the as-synthesized particles was studied using methylene blue dye degradation assay under AMF exposure. With the coatings of these small molecules, the IONPs induced ROS generation was significantly decreased because of the dense surface coverage. To study the effect of polymeric coatings, a degradable poly (beta amino ester) (PBAE) polymer coating was synthesized with dopamine as an anchor to bind to nanoparticles. The surface reactivity of the particles was expected to be recovered once the polymer coating was degraded. Furthermore, the impact of non-degradable PEG-based polymer coating on surface reactivity via ROS generation was also investigated using methylene blue decolorization assay with the presence of AMF. The retention of surface reactivity of PEG-based polymer coated IONPs shows promise for cancer treatment.
The application of IONPs as heterogeneous catalyst for organic contaminant degradation was investigated. Bisphenol A (BPA) was used as a model compound, and Fenton reactions were induced by IONPs with the presence of hydrogen peroxide and hydroxylamine as well as alternating magnetic field exposure. The kinetics of BPA degradation under water bath and AMF exposure at 37oC was also studied, and the results showed potential applications of IONPs for organic pollutants remediation.
37
Pirilä, M. (Minna). "Adsorption and photocatalysis in water treatment:active, abundant and inexpensive materials and methods." Doctoral thesis, Oulun yliopisto, 2015. http://urn.fi/urn:isbn:9789526207629.
Full textAbstract:
Abstract Water contamination is a global problem and the growing utilization of limited water resources creates a need for efficient purification methods. Industrial effluents are polluting the natural waters, e.g. uncontrolled mining activities in developing countries have created numerous environmental hazards and different types of pollutants. This study focuses on novel adsorbents and photocatalytic materials in order to reach the aim of more efficient and affordable water treatment. This thesis aimed at making active, efficient, and viable adsorbents out of waste materials, as well as using photocatalysis in water treatment for organic pollutants originating from different types of industries. Local Peruvian agro-waste was used as a precursor for activated carbon that was used in adsorption studies for single (As(V) and methylene blue, MB), and multicomponent mixtures (As(V)/Pb/Cd), and real polluted river water. An industrial intermediate product, hydrous TiO2, was used for As(III)/As(V) removal. Photocatalytic materials included a commercial photoactive TiO2 (P25), and tailor-made TiO2 based nanofibers (NF) decorated with Pt/Pd. The results show that the agro-waste based activated carbons show high potential as adsorbents (e.g. ~100% As(V) removal in 2 h). With the multicomponent solution there is evidently competition for the adsorption sites; Pb was removed most efficiently. The specific surface area and pore size distribution play an important role in MB adsorption, as with As(V) the ash content is the most influential parameter. The industrial intermediate product has a high adsorption capacity towards both As(III) and As(V) (over 96% removals in 4 h), and is promising for use in natural and wastewater treatment due to its adsorption properties, availability, low cost, and non-toxicity. Photocatalysis was found to be an efficient removal method for the pollutants tested, also in the diluted industrial wastewater matrix, e.g. diuron was removed 99% in 1 h. The NFs are promising for the efficient photocatalytic degradation of organic effluents in aqueous streams such as wastewaters originating from e.g. biofuel production or fine chemicals and pharmaceutical industry. This study provides new and valuable knowledge for the purification of waters, especially when aiming at developing inexpensive water treatment materials and methods for different applicationsTiivistelmä Puhtaan veden puute on maailman laajuinen ongelma, ja raskasmetallien ja orgaanisten haitta-aineiden päätymistä ympäristöön ja luonnonvesiin voidaan vähentää hyvällä ja tehokkaalla teollisuuden jätevesien käsittelyllä. Uusia ja tehokkaita, ympäristön kannalta suotuisia ja kestäviä vedenpuhdistustekniikoita tarvitaan erityisesti kehitysmaissa, joissa esim. kontrolloimaton kaivostoiminta aiheuttaa ympäristö- ja terveyshaittoja. Työn kokeellisessa osassa valmistettiin perulaisesta maatalousjätteistä aktiivihiiltä kemiallisella aktivoinnilla, ja seurattiin niiden kykyä adsorboida haitta-aineita (As(V), Pb, Cd, metyleenisini) yksi- ja monikomponenttiliuoksista ja saastuneesta luonnonvedestä (Puyango-Tumbesjoki, Peru). Lisäksi tutkittiin teollisuuden välituotteen (TiO2) aktiivisuutta arseenin, As(III) ja As(V), adsorptiossa. Viimeisessä osiossa tutkittiin valokatalyysiä orgaanisten haitta-aineiden poistossa vesiliuoksista sekä kaupallisella TiO2 P25 -katalyytillä että kokeellisilla Pd/Pt-dopatuilla TiO2 -nanokuiduilla. Tulokset osoittavat, että paikallisesta raaka-aineesta valmistetut aktiivihiilet ovat hyvin potentiaalisia vedenpuhdistusmateriaaleja saavuttaen jopa 100% As(V) poistuman (2h). Adsorboitavien ionien välillä on nähtävissä kilpailua monikomponettiadsorptiossa; lyijyn havaittiin poistuvan tehokkaimmin tutkituissa olosuhteissa. Adsorbentin ominaispinta-ala ja huokoskokojakauma ovat tärkeitä tekijöitä metyleenisinin adsorptiossa, kun taas tuhkapitoisuudella on arseenin adsorptioon suurempi vaikutus. Teollisuuden TiO2-välituotteella havaittiin olevan korkea adsorptiokapasiteetti sekä As(III)- että As(V)-spesieksiä kohtaan saavuttaen yli 96% poistumat (4h). Se on lupaava materiaali edelleen kehitettäväksi ja käytettäväksi esimerkiksi luonnonvesien ja jätevesien puhdistuksessa johtuen sen hyvistä adsorptio-ominaisuuksista, saatavuudesta, edullisuudesta ja myrkyttömyydestä. Valokatalyysin havaittiin olevan toimiva menetelmä orgaanisten molekyylien hajottamiseen, myös laimeasta teollisuuden jätevesimatriisista, esim. diuroni poistui 99% tunnissa. Nanokuitujen tapauksessa aktiivinen metalli vaikutti merkittävämmin reaktion tehokkuuteen kuin ominaispinta-ala. Tämä työ tarjoaa uutta ja tärkeää tietoa vesien puhdistukseen kun tavoitteena on löytää tehokas ja edullinen menetelmä erityyppisiin sovelluksiin
38
Wilson, Gregory J. "Photocatalysis with a Heterosupramolecular Assembly." Queensland University of Technology, 2006. http://eprints.qut.edu.au/16290/.
Full textAbstract:
Supramolecular chemistry has asserted itself as a significant multidisciplinary field concerned with molecular effects afforded through non-covalent molecular interactions. The increased interest in the literature towards nanoscale devices, through modulation of molecular function, has seen the renaissance of supramolecular chemistry as function progresses from solution to surface. Heterosupramolecular chemistry follows the architectural principles of supramolecular chemistry and embraces both covalent and non-covalent interactions of condensed phase surfaces and molecular components. A modular approach to device architecture was applied as a novel method of performing photocatalysis under visible light illumination. The application of heterosupramolecular assembly to the design of photoelectrochemical cells capable of visible light induced charge separation allowed the study of interfacial processes by means of electrochemical observations. Preparation of a series of supramolecular components was undertaken as specific molecular species within a photochemical system. Starting from a synthesised bidentate ligand that incorporated an acidic functional group, 4,4'-bis(methyl)phosphonate-2,2'-bipyridine (dmpbpy) as its ethyl ester, was chelated to give the surface sensitisers, bis-(2,2'-bipyridine)-(4,4'-bis(methyl)phosphonato-2,2'-bipyridine)ruthenium(II) dichloride ([Ru(bpy)2(dmpbpy)]Cl2) and cis-bis-(4,4'-bis-(methyl)phosphonato-2,2'-bipyridine)(2,2'-bipyridine)ruthenium(II) dichloride ([Ru(dmpbpy)2(bpy)]Cl2). An electron relay moiety with an acidic functional group, 1-ethyl-1'-(2-phosphonoethyl)-4,4'-bipyridinium dichloride (EVP), was also prepared using a procedure developed by the candidate. The electronic properties of the prepared photosensitisers were examined by theoretical quantum chemical TD-DFT calculations on the molecular structures and singlet excitations were discussed in relation to experimental data. This identified that the lowest lying LUMO states were consistently occupied by 2,2'-bipyridine (bpy) and this was speculated to be a factor affecting quantum injection yields. The effect of microwave modification of colloidal TiO2 suspensions under extended periods of treatment was investigated. Nanoparticles of TiO2 were compared and contrast to similar convection hydrothermally treated TiO2 and a commercial titania product, namely Degussa P25, both of which are utilised in device fabrication. The investigation identified that extended periods of microwave hydrothermal treatment do not greatly enhance the crystallinity and primary grain size of TiO2. The heterosupramolecular assembly of a multi-component photochemical system was constructed from prepared molecular and condensed phase components. It was demonstrated that this device was capable of inducing a photochemical reaction in H2O under irradiation with > 420 nm in the absence of an organic electron donor. Interpretation of the photocurrents obtained from this assembly provided understanding of photochemical reactions under low light intensities. Optimised conditions for the photochemical reaction was determined to be pH = 5 and illumination yielded = 0.0036% with an apparent quantum yield (AQY) = 1.6%. Photocatalytic decomposition of organic compounds in a dye-sensitised photoelectrocatalytic cell was investigated for the complete mineralisation of EDTA into CO2, H2 and simple amines and interpreted through photocurrent observations. This was extended to a broad range of organic compounds of various solution concentrations as a simulated industrial waste stream. Photooxidation gave unique photocurrent-time profiles which identified two distinct interfacial processes by mathematical treatment of photocurrent transients with a kinetic model. Kinetic parameters were proposed as a factor for qualitative discrimination of the organic compounds. The implications of these results for heterogeneous catalysis were discussed and the formation of Host-Guest complexes as a method of molecular sensing and as specific photocatalytic receptors was proposed.
39
Yang, Congqiao. "Persistent organic pollutants in lacustrine environments." Thesis, University of Birmingham, 2014. http://etheses.bham.ac.uk//id/eprint/5030/.
Full textAbstract:
Water samples taken from nine English freshwater lakes from a mix of urban, rural, and remote locations on 13 occasions between April 2008 and February 2012 were analysed for selected non-dioxin like-PCBs, tri- through hexa-PBDEs, and the three main HBCD diastereomers (\(\alpha\)-, \(\beta\)-, and \(\gamma\)-HBCD). Concentrations of PCBs and HBCDs declined over the sampling period with half-lives of 3.8 and 5.1 years, respectively. In addition, concentrations of PCBs, HBCDs, tri- through deca-BDEs, and 32 selected NBFRs were measured in radiometrically-dated sediment core slices taken in summer 2011/2 from seven of the same English lakes. Temporal trends in contamination with “legacy” POPs generally accord with historical trends in UK manufacture and use, with PCB contamination at all lakes increasing from ~1950, peaking generally between the late-1960s and mid-1980s, before declining steadily thereafter. In contrast, at most sites, BDE-209 displayed generally smooth increases following its initial emergence, and showed no obvious levelling off trend. Contamination with some NBFRs displayed significantly increasing trends. Spatial variation in POPs contamination of the lakes studied was evident; with regression analysis suggesting concentrations are higher in lakes with surface areas that are small relative to their catchment area, and that are closer to areas of high population density. The estimated PCB burden in the British environment is 521 tons, with TBPH (281 tons) and BDE-209 (147 tons) following not far behind. Estimated UK burdens of the remaining target compounds were significantly lower.
40
Finnilä, M. A. (Mikko A. J. ). "Bone toxicity of persistent organic pollutants." Doctoral thesis, Oulun yliopisto, 2014. http://urn.fi/urn:isbn:9789526205090.
Full textAbstract:
Abstract Persistent organic pollutants (POPs), especially dioxin-like chemicals, have been shown to have adverse effects on skeleton and these effects are likely to be mediated via the aryl hydrocarbon receptor (AHR). In spite of the extensive research, the characteristics of developmental effects of POPs are poorly known and the role of AHR in POP bone toxicity and skeletal development in general. In this project changes in bone morphology and strength as well as tissue matrix mechanics are studied by applying state of the art biomedical engineering methods. This allows understanding of the effects of dioxins exposure and AHR activity on the development and maturation of extracellular matrix in musculoskeletal tissues from a completely new perspective, and thereby improving the health risk assessment of POPs. In the present study skeletal properties of rats exposed maternally to 2,3,7,8-tetrachlorodibenzo-p-dioxin (TCDD), Northern Contaminant Mixture (NCM) and Aroclor1254 (A1254) were studied for cross-sectional morphometric and biomechanical properties, and data were analysed with benchmark dose modelling. In addition, extracellular matrix properties were analysed using nanoindentation. Similar measurements were performed for adult wild-type and AHR-null mice after TCDD exposure. The same animals were also analysed for microstructural changes using micro-computed tomography and their bone cell activity was estimated from serum markers and gene expression. Analyses show decreased bone length and cross-sectional properties with consequently decreased bone strength. On the other hand, an increased trabecular BMD in response to NCM and A1254 was observed. In addition, bone matrix properties indicated delayed maturation or early senescence after maternal or adult exposure, respectively. The AHR is mainly responsible for bone toxicity of dioxin-like compounds and plays a role in bone development. This is likely due to disturbed bone remodeling as indicated by altered serum markers and gene expression. Overall these results indicate that POPs decrease bone strength, but the interpretation is difficult as there is more trabecular bone within cortical bone with compromised quality and increased porosityTiivistelmä Altistumisen pysyville orgaanisille ympäristökemikaaleille on todettu heikentävän luustoa. Dioksiinien ja dioksiininkaltaisten yhdisteiden vaikutusten on havaittu välittyvän aryylihiilivetyreseptorin (AHR) välityksellä. Huolimatta pitkään kestäneestä tutkimuksesta POP-yhdisteiden sikiönkehityksen aikaisen altistuksen vaikutukset ja etenkin niiden mekanismit ovat edelleen huonosti tunnettuja, samoin kuin AHR:n osuus POP-yhdisteiden luutoksisuudessa ja luuston kehityksessä ylipäätään. Tässä työssä tutkittiin luuston rakenteellisia ja mekaanisia ominaisuuksia niin perinteisillä kuin uusimmilla biolääketieteen tekniikan menetelmillä. Tutkimuksen tavoitteena on saada uutta tietoa POP-altistuksen ja AHR-aktiivisuuden vaikutuksista luuston kehitykseen ja luukudoksen ikääntymisprosesseihin, mikä edesauttaa kyseisten yhdisteiden riskinarviointia. Tutkimuksissa altistettiin kantavia rottaemoja 2,3,7,8-tetraklooridibenzo-p-dioksiinille (TCDD), pohjoiselle saasteseokselle ja kaupalliselle Arokloori 1254 PCB-seokselle. Sikiönkehityksen aikana altistuneiden jälkeläisten luuston poikkileikkausen morfologia ja biomekaaniset ominaisuudet mitattiin ja tulokset mallinnettiin vertailuannoksen määrittämiseksi. Lisäksi TCDD-altistettujen rottien luustomatriisin ominaisuuksia selvitettiin nanoindentaatiomenetelmällä. Samaa menetelmää käytettiin myös aikuisiässä TCDD:lle altistettujen villityypin hiirten ja AHR-poistogeenisiten hiirten tutkimiseen. Näiden hiirten luuston hienorakennetta mitattiin myös korkean resoluution mikro-tietokonetomografialla ja niiden luusolujen aktiivisuutta tutkittiin seerumin biomarkkerien ja luun muodostumiseen osallistuvien geenien ekspressiotasojen avulla. Sikiönkehityksen aikainen altistuminen pohjoiselle saasteseokselle ja Arokloori 1254:lle hidasti luiden pituuskasvua. Lisäksi luiden poikkileikkauspinta-alat olivat pienentyneet ja mekaaniset ominaisuudet heikentyneet. Toisaalta hohkaluun määrä oli lisääntynyt altistumisen seurauksena. Myös sikiönkehityksen aikainen altistuminen TCDD:lle hidasti luukudoksen kypsymistä ja johti aikuisiällä luukudoksen ennenaikaiseen vanhenemiseen. AHR:llä oli päärooli ainakin aikuisiän vaikutusten ilmenemiselle ja reseptorilla vaikutti olevan rooli luuston kehityksessä ylipäätään. Seerumin biomarkkereiden ja geeniekspression muutosten perusteella nämä vaikutukset johtuvat todennäköisesti luuston uusiutumisen häiriöistä. Yhteenvetona voidaan todeta, että POP-yhdisteet heikentävät luustoa, mutta tämän ilmiön diagnosoiminen on hankalaa, koska huonolaatuisen kuoriluun sisällä hohkaluun määrä on lisääntynyt
41
清家, 伸康, and 新太 片山. "Monitoring and Remediation of Persistent Organic Pollutants." 日本農薬学会, 2007. http://hdl.handle.net/2237/10923.
Full text
42
Subramani, Arun. "ADSORPTION OF ORGANIC POLLUTANTS ONTO NATURAL ADSORBENTS." MSSTATE, 2002. http://sun.library.msstate.edu/ETD-db/theses/available/etd-08102002-210619/.
Full textAbstract:
In this research, the adsorptive capacities of kenaf, peat moss, hay, and peanut hulls were evaluated for the removal of TNT and 2,4-DCP from aqueous solutions. Adsorbent loading capacities determined by batch studies were verified by continuous column experiments. It was found that the adsorption capacity of the candidate adsorbents were significantly lower than granular activated carbon (GAC). The impact of surface modification techniques, such as surface oxidation, were evaluated to study the effect on adsorption capacity. At lower equilibrium concentrations of the adsorbate (less than 10 ppb), surface oxidation by ozone showed an increase in the adsorption capacity. The same trend was not observed with peroxone and ultrasound pretreatment. The adsorbent requirement for treating water contaminated with TNT and 2,4-DCP were calculated based on the adsorptive capacity of the adsorbents. Though the adsorbent requirements for the candidate adsorbents were considerably higher than granular activated carbon, the adsorbent requirement costs for most of the candidate adsorbents tested were competitive when compared to GAC costs.
43
Paul, Jessica Marie. "Behavior of organic pollutants in Arctic sediments /." Click here for download, 2008. http://proquest.umi.com/pqdweb?did=1436385051&sid=1&Fmt=2&clientId=3260&RQT=309&VName=PQD.
Full text
44
Zhou, Qixin. "Flow Accelerated Organic Coating Degradation." Diss., North Dakota State University, 2014. https://hdl.handle.net/10365/27242.
Full textAbstract:
Applying organic coatings is a common and the most cost effective way to protect metallic objects and structures from corrosion. Water entry into coating-metal interface is usually the main cause for the deterioration of organic coatings, which leads to coating delamination and underfilm corrosion. Recently, flowing fluids over sample surface have received attention due to their capability to accelerate material degradation. A plethora of works has focused on the flow induced metal corrosion, while few studies have investigated the flow accelerated organic coating degradation. Flowing fluids above coating surface affect corrosion by enhancing the water transport and abrading the surface due to fluid shear. Hence, it is of great importance to understand the influence of flowing fluids on the degradation of corrosion protective organic coatings. In this study, a pigmented marine coating and several clear coatings were exposed to the laminar flow and stationary immersion. The laminar flow was pressure driven and confined in a flow channel. A 3.5 wt% sodium chloride solution and pure water was employed as the working fluid with a variety of flow rates. The corrosion protective properties of organic coatings were monitored inline by Electrochemical Impedance Spectroscopy (EIS) measurement. Equivalent circuit models were employed to interpret the EIS spectra. The time evolution of coating resistance and capacitance obtained from the model was studied to demonstrate the coating degradation. Thickness, gloss, and other topography characterizations were conducted to facilitate the assessment of the corrosion. The working fluids were characterized by Fourier Transform Infrared Spectrometer (FTIR) and conductivity measurement. The influence of flow rate, fluid shear, fluid composition, and other effects in the coating degradation were investigated. We conclude that flowing fluid on the coating surface accelerates the transport of water, oxygen, and ions into the coating, as well as promotes the migration of coating materials from the coating into the working fluid, where coatings experience more severe deterioration in their barrier property under flowing conditions. Pure water has shown to be a much more aggressive working fluid than electrolyte solutions. The flowing fluid over the coating surface could be used as an effective acceleration method.NDSU Advance FORWARD Program; NSF HRD-0811239
45
Akinyeye, Richard Odunayo. "Nanostructured polypyrrole impedimetric sensors for anthropogenic organic pollutants." Thesis, University of the Western Cape, 2007. http://etd.uwc.ac.za/index.php?module=etd&action=viewtitle&id=gen8Srv25Nme4_5301_1248150815.
Full textAbstract:
The main aim of this study was to develop a novel strategy for harnessing the properties of electroconductive polymers in sensor technology by using polymeric nanostructured blends in the preparation of high performance sensor devices.
46
Raff, Jonathan Daniel. "Transport of organic pollutants and their atmospheric fates." [Bloomington, Ind.] : Indiana University, 2007. http://gateway.proquest.com/openurl?url_ver=Z39.88-2004&rft_val_fmt=info:ofi/fmt:kev:mtx:dissertation&res_dat=xri:pqdiss&rft_dat=xri:pqdiss:3292440.
Full textAbstract:
Thesis (Ph. D.)--Indiana University, School of Public and Environmental Affairs, 2007.Title from dissertation home page (viewed May 28, 2008). Source: Dissertation Abstracts International, Volume: 68-11, Section: B, page: 7189. Adviser: Ronald A. Hites.
47
Cousins, Ian T. "Air-soil exchange of persistent organic pollutants (POPs)." Thesis, Lancaster University, 1998. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.310506.
Full text
48
Hunter, Paige Holt. "Control of Volatile Organic Compound (VOC) Air Pollutants." Diss., Virginia Tech, 2000. http://hdl.handle.net/10919/38614.
Full textAbstract:
A variety of methods exist to remove volatile
organic compound (VOC) air pollutants from
contaminated gas streams. As regulatory and
public opinion pressures increase, companies are
searching for more effective methods to control
these emissions. This document is intended as a
guide to help determine if existing systems are
adequate and to provide additional information to
improve the efficiency of the systems. It
explores conventional methods of controlling VOC
emissions, as well as innovative technologies
including membrane separation, plasma destruction,
and ozone catalytic oxidation. The conventional
technologies covered include condensation,
adsorption, absorption (or scrubbing), thermal
incineration, flaring, catalytic incineration,
and biofiltration. Each chapter includes a
description of the technology, a discussion of
the types of systems available, notes on the
design of the system, economic estimates, an
explanation of potential problems, and a list of
considerations for installation and maintenance
concerns. The final chapter is dedicated to the
preparation and characterization of metal
catalysts which were developed to improve the
reaction rate of VOCs using ozone as an oxidant.Ph. D.
49
Koskela, A. (Antti). "Bone as a target for persistent organic pollutants." Doctoral thesis, Oulun yliopisto, 2016. http://urn.fi/urn:isbn:9789526214306.
Full textAbstract:
Abstract Persistent organic pollutants (POPs) are ubiquitous and bioaccumulative man-made chemicals, resistant to chemical, biological and photolytic degradation and widely distributed to sediments, wildlife, and human. Many of these chemicals have adverse effects on a variety of targets, including the endocrine system, organogenesis and reproduction. Due to these effects and wide distribution, many of them are either banned or strictly controlled. However, because of persistency, they continue to interact with organisms globally. Despite the existing knowledge of the adverse effects of POPs, the effects of many chemicals on bone tissue are still poorly known. In the present study, we investigated the adverse effects of three common POPs, including tributyltin (TBT), 2,3,7,8-tetrachlorodibenzo-p-dioxin (TCDD) and perfluorooctanoic acid (PFOA) on the skeletal system. In vitro models were used to study the effects of PFOA in mouse and in human, and the co-effects of TBT and TCDD on differentiating osteoblasts and osteoclasts of mice. An in vivo model for mice was used to study the developmental effects of maternal PFOA-exposure on pups among with morphometrical and biomechanical property analyses. Mass-spectrometry was used to study the presence of PFOA in bones both in mice and in human, the latter acquired from the bone bank held in the Oulu University Hospital, Finland. The bones were also analyzed with cone beam computer tomography and microcomputer tomography. The results show that PFOA exposure in utero and during lactation leads to the accumulation of PFOA in bone, traceable even 17 months after exposure. PFOA exposure decreased the mineral density of the tibias and increased the medullary area. Nearly all of the human samples contained PFAS, including PFOA. PFOA also disturbed the differentiation of osteoblasts and with lower doses, increased bone resorption of osteoclasts both in mouse and human, the phenomenon being slightly stronger in mice. Co-exposure to TBT and TCDD led to decreased differentiation of osteoblasts and osteoclast, and the co-effect was partially synergistic in osteoblasts. These results show disruption of bone development, bone cell differentiation, and PFAS accumulation in bone. Further studies are recommended to evaluate the co-effects of different POPs and the possible effects of long-term accumulation of POPs in bone and other tissuesTiivistelmä Pysyvät orgaaniset ympäristömyrkyt (POP-yhdisteet) ovat kemikaaleja, jotka ovat levinneet ihmisen toiminnan seurauksena laajalle ympäristöön, sen eliöihin ja ihmisiin. Monilla POP-yhdisteillä on haitallisia vaikutuksia esimerkiksi hormonaaliseen toimintaan, elinten muodostukseen ja hedelmällisyyteen. Toksisten vaikutusten ja niiden yleisyyden vuoksi monien POP-yhdisteiden käyttö on joko rajattua tai kielletty kokonaan. Laajan levinneisyytensä ja hitaan puoliintumisaikansa takia POP-yhdisteet ovat kuitenkin edelleen vuorovaikutuksessa ympäristön ja sen eliöiden kanssa. POP-yhdisteiden luustovaikutuksista tiedetään edelleen vähän. Tässä väitöskirjassa tutkittiin kolmen yleisen POP-yhdisteen, tributyylitinan (TBT), 2,3,7,8-tetraklooridibentso-p-dioksiinin (TCDD) ja perfluoro-oktaanihapon (PFOA), vaikutuksia luustoon. PFOA:n vaikutuksia hiiren ja ihmisen luustoon sekä TBT:n ja TCDD:n yhteisvaikutuksia hiiren erilaistuvien osteoblastien ja osteoklastien suhteen selvitettiin in vitro -malleilla. In vivo -mallilla tutkittiin hiiriemon PFOA-altistuksen vaikutusta syntyvien poikasten luuston kehitykseen ja remodelaatioon analysoimalla poikkileikekuvia sekä luiden biomekaanisia ominaisuuksia. Lisäksi luiden PFOA-pitoisuudet mitattiin massaspektrometrilla. Tutkimusta laajennettiin ihmiseen analysoimalla Oulun yliopistollisen sairaalan luupankkinäytteitä. Ihmisnäytteet analysoitiin myös kartiokeila-TT:n ja mikro-TT:n avulla. Tulosten mukaan PFOA kertyy luuhun; hiiriltä voitiin mitata PFOA-pitoisuuksia jopa 17 kuukautta altistumisen jälkeen. Lisäksi PFOA-altistus pienensi luun mineraalitiheyttä ja kasvatti luuydinontelon tilavuutta. Lähes kaikki ihmisluunäytteet sisälsivät PFOA:ta ja muita PFAS-yhdisteitä. Solukokeiden perusteella PFOA-altistus häiritsee osteoblastien erilaistumista ja pienillä pitoisuuksilla lisää osteoklastien luunhajotusta sekä hiirellä että ihmisellä. TBT:n ja TCDD:n yhteisaltistus vaikuttaa puolestaan vähentävän sekä osteoblastien että osteoklastien erilaistumista ja toimintaa; osteoblastien osalta yhteisvaikutus oli osaksi synergistinen. Väitöskirja antaa lisätietoa POP-yhdisteiden vaikutuksista luun kehitykseen ja luusolujen erilaistumiseen sekä PFAS-yhdisteiden kertymisestä luuhun. Väitöksessä myös suositellaan lisätutkimuksia yhdisteiden yhteisvaikutuksista sekä pitkän aikavälin ympäristökemikaalikertymän vaikutuksista luussa ja muissa kudoksissa
50
Leat, Eliza Helen Kelsey. "Persistent organic pollutants in great skuas Stercorarius skua." Thesis, University of Glasgow, 2013. http://theses.gla.ac.uk/4192/.
Full textAbstract:
The bioaccumulation of persistent organic pollutants (POPs) is of particular environmental concern in top predators, which accumulate high concentrations of POPs that can cause adverse effects. Previous small scale studies found high concentrations of POPs in adult great skuas, Stercorarius skua, a top predator in the marine environment. This thesis investigates the factors affecting concentrations and patterns of POPs (contribution of individual POPs to the ΣPOPs) in the great skua across its breeding range in the north-east Atlantic. Clear differences between colonies in both concentration and pattern of POPs in adult plasma were not indicative of being caused by long range transport of POPs in the atmosphere. Variation in diet between colonies is the mostly likely explanation for these colony differences, with great skuas from some colonies having a greater proportion of fish in their diet whilst others eat more seabird prey. Although seabirds are often used in studies of POPs in the environment, the effect of migratory behaviour has not previously been studied in detail. By using a combination of global location sensor (GLS) loggers and feather stable isotopes from winter grown feathers, the wintering areas of individuals from three breeding populations of great skuas were identified. Great skuas spend the winter in three distinct areas across the North Atlantic, with birds from the same breeding colonies wintering in different areas. In two of the three breeding populations, wintering area explained a significant proportion of variation in organochlorines (OCs) concentrations and pattern. However in the colony with the highest concentrations of OCs, no effect of wintering area was found, possibly as a result of these great skuas feeding at a higher trophic level during the breeding season than other populations. Temporally, concentrations of OCs were higher in 1980 than 2008 in eggs, whilst newer contaminants polybrominated diphenyl ethers (PBDEs) and perfluorinated chemicals (PFASs) show the opposite trend. In conclusion, concentrations of POPs in the great skua were influenced primarily by breeding season diet with wintering area and sex also having small but significant effects on POPs. Wintering area explained the most variation in the pattern of POPs in great skuas. The POP concentrations found in this study exceeded those which have been found to cause adverse effects on the immune system and reproduction in other species of seabird.