Philosophiae Doctor - PhD / Persistent organic pollutants (POPs) are very tenacious wastewater contaminants with negative impact on the ecosystem. The two major sources of POPs are wastewater from textile industries and pharmaceutical industries. They are known for their recalcitrance and circumvention of nearly all the known wastewater treatment procedures. However, the wastewater treatment methods which applied advanced oxidation processes (AOPs) are documented for their successful remediation of POPs. AOPs are a group of water treatment technologies which is centered on the generation of OH radicals for the purpose of oxidizing recalcitrant organic contaminants content of wastewater to their inert end products. Circumvention of the reported demerits of AOPs such as low degradation efficiency, generation of toxic intermediates, massive sludge production, high energy expenditure and operational cost can be done through the application of the combined AOPs in the wastewater treatment procedure. The resultant mineralisation of the POPs content of wastewater is due to the synergistic effect of the OH radicals produced in the combined AOPs. Hydrodynamic cavitation is the application of the pressure variation in a liquid flowing through the venturi or orifice plates. This results in generation, growth, implosion and subsequent production of OH radicals in the liquid matrix. The generated OH radical in the jet loop hydrodynamic cavitation was applied as a form of advanced oxidation process in combination with hydrogen peroxide, iron (II) oxides or the synthesized green nano zero valent iron (gnZVI) for the treatment of simulated textile and pharmaceutical wastewater.

The use of nano zerovalent iron (nZVI) for environmental remediation is a promising new technique for in situ remediation. Due to its high surface area and high reactivity, nZVI is able to dechlorinate organic contaminants and render them harmless. Limited mobility, due to fast aggregation and sedimentation of nZVI, limits the capability for source and plume remediation. Carbo-Iron is a newly developed material consisting of activated carbon particles (d50 = 0,8 µm) that are plated with nZVI particles. These particles combine the mobility of activated carbon and the reactivity of nZVI. This paper presents the rst results of the transport experiments. / Der Einsatz von elementarem Nanoeisen ist eine vielversprechende Technik zur Sanierung von Altlastenschadensfällen. Aufgrund der hohen Oberäche und der hohen Reaktivität kannn ZVI chlororganische Schadstoffe dechlorieren und zu harmlosen Substanzen umwandeln. Der Einsatz von Nanoeisen zur Quellen- und Fahnensanierung wird jedoch durch mangelnde Mobilität im Boden im eingeschränkt. Carbo-Iron ist ein neu entwickeltes Material, das aus Aktivkohlepartikeln (d50 = 0,8 µm) und nZVI besteht. Diese Partikel kombinieren die Mobilit ät von Aktivkohle mit der Reaktivität von nZVI. Dieser Artikel beschreibt erste Ergebnisse von Transportuntersuchungen.

<p>Ekolo&scaron;ki&nbsp; problem&nbsp; svetskih&nbsp; razmera&nbsp; predstavlja&nbsp; zagađenost&nbsp; sedimenta&nbsp; te&scaron;kim&nbsp; metalima, usled negativnih ekolo&scaron;kih efekata metala na životnu sredinu. Mnoge zemlje i regioni, kao i na&scaron;a zemlja&nbsp; suočavaju&nbsp; se&nbsp; sa&nbsp; ovom&nbsp; problematikom,&nbsp; koja&nbsp; je&nbsp; vrlo&nbsp; rasprostranjena&nbsp; usled&nbsp; sve&nbsp; brže urbanizacije&nbsp; i&nbsp; industrijalizacije,&nbsp; a&nbsp; sa&nbsp; sve&nbsp; većom&nbsp; nebrigom&nbsp; usled&nbsp; ispu&scaron;tanja&nbsp; otpadnih&nbsp; voda&nbsp; bez prethodnog&nbsp; preči&scaron;ćavanja&nbsp; u&nbsp; vodotokove.&nbsp; Prilikom&nbsp; promene&nbsp; uslova&nbsp; vodenog&nbsp; ekosistema,&nbsp; može doći do&nbsp; izluživanja&nbsp; metala&nbsp; i &scaron;tetnih efekata na&nbsp; životnu sredinu kao&nbsp; i&nbsp; na zdravlje&nbsp; ljudi. Stoga je remedijacija sedimenata zagađenih metalima ključna aktivnost u okviru procesa potpune sanacije vodenog ekosistema, a ekonomične, efikasne i ekolo&scaron;ki prihvatljive tehnike remedijacije su hitno potrebne&nbsp; i&nbsp; rado&nbsp; primenljive&nbsp; u&nbsp; tretmanu&nbsp; na&nbsp; velikoj&nbsp; skali.&nbsp; Pre&nbsp; primene&nbsp; remedijacione&nbsp; tehnike&nbsp; na velikoj skali, neophodna su ispitivanja pri laboratorijskim uslovima i pilot skali.&nbsp; Na kraju svakog uspe&scaron;nog&nbsp; laboratorijskog&nbsp; ispitivanja&nbsp; nalaze&nbsp; se&nbsp; pilot&nbsp; istraživanja.&nbsp; Pomoću&nbsp; njih&nbsp; se&nbsp; dobija&nbsp; p ravi odgovor u smislu izbora optimalne tehnologije imajući u vidu investicione i operativne tro&scaron;kove,<br />postignuti rezultat i krajnje ciljeve u pogledu upravljanja postrojenjem i otpadom. U ovom radu ispitan&nbsp; je&nbsp; potencijal&nbsp; primene&nbsp; stabilisanog&nbsp; i&nbsp; zelenom&nbsp; sinte zom&nbsp; produkovanog&nbsp; nano&nbsp; Fe(0)&nbsp; zaremedijaciju&nbsp; sedimenta&nbsp; zagađenog&nbsp; te&scaron;kim&nbsp; metalima.&nbsp; Kao&nbsp; remedijaciona&nbsp; tehnika&nbsp; odabrana&nbsp; je stabilizacija/solidifikacija,&nbsp; koja&nbsp; podrazumeva&nbsp; dodavanje&nbsp; agenasa&nbsp; za&nbsp; imobilizaciju&nbsp; metala&nbsp; u sedimentu&nbsp; sprečavajući&nbsp; time&nbsp; potencijalni&nbsp; rizik&nbsp;&nbsp; od&nbsp; izluživanja&nbsp; metala&nbsp; u&nbsp; životnu&nbsp; sredinu. Konvencionalni&nbsp; materijali&nbsp; poput&nbsp; letećeg&nbsp; pepela,&nbsp; cementa,&nbsp; gline&nbsp; se&nbsp; već&nbsp; odavno&nbsp; koriste&nbsp; u&nbsp; ovu svrhu. Kako u dana&scaron;nje vreme raste potražnja za novim, lako dostupnim agensima za stabilizaciju<br />sedimenta, do&scaron;lo se na ideju o primeni nanomaterijala na bazi gvožđa, tj. nano Fe(0) stabilisanog nativnom glinom&nbsp; i produkovanog redukcijom pomoću organskih&nbsp; molekula prirodno prisutnih u ekstraktu&nbsp; li&scaron;ća&nbsp; hrasta&nbsp; i&nbsp; crnog&nbsp; duda.&nbsp; Nanomaterijali&nbsp; su&nbsp; sintetisani&nbsp; i&nbsp; karakterisani&nbsp; različitim metodama&nbsp; i&nbsp; tehnikama.&nbsp; U&nbsp; nastavaku,&nbsp; u&nbsp; cilju&nbsp; efikasnosti&nbsp; njihove&nbsp; primene&nbsp; za&nbsp; stabilizaciju sedimenta, sprovedeni su ekstrakcioni i dinamički laboratorijski testovi izluživanja. Odabrane su sme&scaron;e sedimenta i nanomaterijala koje su pokazale najbolju efikasnost tr etmana. Nakon toga se ispitivanje&nbsp; nastavilo&nbsp; na&nbsp; pilot&nbsp; skali,&nbsp; gde&nbsp; se&nbsp; pratilo&nbsp; pona&scaron;anje&nbsp; nanomaterijala&nbsp; u&nbsp; zavisnosti&nbsp; od konvencionalnih&nbsp; materijala&nbsp; koji&nbsp; su&nbsp; već&nbsp; u&nbsp; literaturi&nbsp; dokumentovani&nbsp; kao&nbsp; efikasni&nbsp; imobilizacioni agensi. Dodatna potvrda uspe&scaron;nosti tretmana data je analizom i karakterizacijom s/s sme&scaron;a nakon pilot&nbsp; ispitivanja&nbsp; Na&nbsp; osnovu&nbsp; dobijenih&nbsp; rezultata&nbsp; proces&nbsp; se&nbsp; uspe&scaron;no&nbsp; pokazao&nbsp; pri&nbsp; laboratorijskim uslovima,&nbsp; a&nbsp; takođe&nbsp; i&nbsp; prilikom&nbsp; pilot&nbsp; tretmana,&nbsp; odnosno&nbsp; nakon&nbsp; pilot&nbsp; tretmana&nbsp; nije&nbsp; do&scaron;lo&nbsp; do povećanih koncentracija&nbsp; izluživanja metala iz s/s sme&scaron;a, kao ni degradacije sme&scaron;a nakon procesa ovlaživanja&nbsp; tokom&nbsp; &scaron;est&nbsp; meseci.&nbsp; Na&nbsp; osnovu&nbsp; toga,&nbsp; ovako&nbsp; tertirani&nbsp; sediment&nbsp; se&nbsp; može&nbsp; bezbedno odlagati&nbsp; na&nbsp; deponije,&nbsp; ili&nbsp; pak&nbsp; iskoristiti&nbsp; za&nbsp; &bdquo;kontrolisanu&ldquo;&nbsp; upotrebu,&nbsp; izgradnju&nbsp; puteva,kamenoloma, pomoćnih objekata i slično. Rezultati su doprineli u cilju trajnijeg re&scaron;avanja pitanja odlaganja&nbsp; zagađenog&nbsp; (izmuljenog)&nbsp; rečnog&nbsp; sedimenta,&nbsp; pri&nbsp; čemu&nbsp; se&nbsp; u&nbsp; procesu stabilizacije/solidifikacije&nbsp; dobijaju&nbsp; proizvodi&nbsp; sa&nbsp; dodatom&nbsp; vredno&scaron;ću&nbsp; neumanjenog&nbsp; kvaliteta .Nanomaterijali sintetisani u ovom radu na&nbsp; bazi ekstrakta li&scaron;ća biljaka doprinose kako očuvanju životne&nbsp; sredine,&nbsp; tako&nbsp; i&nbsp; ekonomičnosti&nbsp; primene&nbsp; remedijacione&nbsp; tehnike.&nbsp; Zahvaljujući&nbsp; velikoj specifičnoj&nbsp; povr&scaron;ini,&nbsp; malim&nbsp; dimenzijama&nbsp; čestica&nbsp; i&nbsp; velikom&nbsp; kapacitetu&nbsp; za&nbsp; imobilizaciju&nbsp; te&scaron;kih<br />metala predstavljaju efikasnu alternativu komercijalno dostupnim materijalima, &scaron;to ih čini veoma atraktivnim&nbsp; i&nbsp; obećavajućim&nbsp; u&nbsp; budućnosti&nbsp; pri&nbsp; tretmanu&nbsp; rečnog&nbsp; sedimenta&nbsp; zagađenog&nbsp; te&scaron;kim metalima.</p> / <p>The pollution of sediment by heavy metals represents a large environmental problem all<br />over the world.&nbsp; A&nbsp; lot of countries&nbsp; in the region&nbsp; as well as our country deal with this problem, which&nbsp; is&nbsp; widespread&nbsp; because&nbsp; of&nbsp; the&nbsp; fast&nbsp; urbanization&nbsp; and&nbsp; industrialization.&nbsp; There&nbsp; is&nbsp; more&nbsp; and more&nbsp; carelessness&nbsp; about&nbsp; wastewater&nbsp; discharge&nbsp; into&nbsp; water&nbsp; flows&nbsp; without&nbsp; previous&nbsp; purification. When the conditions of the aquatic ecosystem change, metal leaching and harmful effects on the environment&nbsp; and&nbsp; human&nbsp; health&nbsp; can&nbsp; occur.&nbsp; Therefore,&nbsp; remediation&nbsp; of&nbsp; metal-contaminated sediments&nbsp; is&nbsp; crucial&nbsp; activity&nbsp; in&nbsp; the&nbsp; process&nbsp; of&nbsp; the&nbsp; complete&nbsp; ecosystem&nbsp; remediation.&nbsp; Cost effective, efficient and environmentally friendly remediation techniques are urgently needed and readily applicable in large-scale treatment. Before applying remediation techniques on the largescale,&nbsp; both&nbsp; laboratory&nbsp; and&nbsp; pilot&nbsp; tests&nbsp; are&nbsp; necessary.&nbsp; There&nbsp; are&nbsp; pilot&nbsp; studies&nbsp; at&nbsp; the&nbsp; end&nbsp; of&nbsp; each successful&nbsp; laboratory&nbsp; test.&nbsp; Those&nbsp; studies&nbsp; provide&nbsp; the&nbsp; right&nbsp; answer&nbsp; in&nbsp; terms&nbsp; of&nbsp; choosing&nbsp; the optimal technology, taking into account the investment and operating costs,&nbsp;&nbsp; the achieved resultand&nbsp; the&nbsp; ultimate&nbsp; goals&nbsp; in&nbsp; terms&nbsp; of&nbsp; plant&nbsp; and&nbsp; waste&nbsp; management.&nbsp; In&nbsp; this&nbsp; study,&nbsp; the&nbsp; application<br />potential of stabilized and green&nbsp; -&nbsp; synthesized&nbsp; nano Fe(0) for the remediation of&nbsp; heavy&nbsp; metal&nbsp; -contaminated&nbsp; sediment&nbsp; was&nbsp; investigated.&nbsp; Stabilization&nbsp; /&nbsp; solidification&nbsp; technique&nbsp; was&nbsp; chosen&nbsp; as remediation technique which involves the addition of metal immobilizing agents in the sediment thus preventing the potential risk of metal leaching into the environment. Conventional materials such as fly ash, cement and clay have long been used for this purpose. Nowadays there is need for new, easily accessible agents for the sediment stabilization. Therefore it came up with the idea of&nbsp; using&nbsp; iron-based&nbsp; nanomaterials,&nbsp; ie.&nbsp; nano&nbsp; Fe(0)&nbsp; stabilized&nbsp; by&nbsp; native&nbsp; cla y&nbsp; and&nbsp; produced&nbsp; by reduction&nbsp; using&nbsp; organic&nbsp; molecules&nbsp; naturally&nbsp; present&nbsp; in&nbsp; oak&nbsp; and&nbsp; black&nbsp; mulberry&nbsp; leaf&nbsp; extract. Nanomaterials have been synthesized and characterized by different methods and techniques. In order&nbsp; to&nbsp; be&nbsp; effective&nbsp; in&nbsp; their&nbsp; application&nbsp; for&nbsp; sediment&nbsp; stabilization,&nbsp; extraction&nbsp; and&nbsp; dynamic laboratory leaching tests were performed. Mixtures of sediment and nanomaterials were selected that showed the best treatment efficiency.&nbsp; After that, the examination was continued on a pilot scale, where the behavior of nanomaterials was monitored, depending on conventional materials which&nbsp; have&nbsp; already&nbsp; been&nbsp; documented&nbsp; in&nbsp; the&nbsp; literature&nbsp; as&nbsp; effective&nbsp; immobilizing&nbsp; agents.Additional confirmation of treatment success was given by analysis and characterization of s / s mixtures&nbsp; after&nbsp; pilot&nbsp; testing.&nbsp; According&nbsp; to&nbsp; obtained&nbsp; results,&nbsp; the&nbsp; process&nbsp; was&nbsp; successfully demonstrated&nbsp; under&nbsp; laboratory&nbsp; conditions,&nbsp; and&nbsp; also&nbsp; during&nbsp; the&nbsp; pilot&nbsp; treatment.&nbsp; After&nbsp; the&nbsp; pilot treatment&nbsp; there&nbsp; were&nbsp; no&nbsp; increased&nbsp; concentrations&nbsp; of&nbsp; metal&nbsp; leaching&nbsp; from&nbsp; s/s&nbsp; mixtures,&nbsp; nor mixture degradation after the wetting process for six months. Based on that, the sediment treated in this way&nbsp; can&nbsp; be safely disposed of&nbsp; in&nbsp; landfills, or used&nbsp; for &quot;controlled&quot; use, construction of<br />roads,&nbsp; quarries,&nbsp; auxiliary&nbsp; facilities&nbsp; and&nbsp; etc.&nbsp; The&nbsp; results&nbsp; have&nbsp; contributed&nbsp; to the&nbsp; goal&nbsp; of&nbsp; a&nbsp; more permanent solution to the issue of disposal of polluted (slugged) river sediment, whereby in the process&nbsp; of&nbsp; stabilization/solidification,&nbsp; products&nbsp; with&nbsp; added&nbsp; value&nbsp; of&nbsp; undiminished&nbsp; quality&nbsp; are obtained. The nanomaterials synthesized in this paper on the basis of plant leaf extract contribute to both the preservation of the environment and the economy of remediation techniques. Thanks to their&nbsp; large specific&nbsp; surface area, small particle size and&nbsp; large ca pacity&nbsp; for&nbsp; immobilization of heavy&nbsp; metals,&nbsp; they&nbsp; represent&nbsp; an&nbsp; effective&nbsp; alternative&nbsp; to&nbsp; commercially&nbsp; available&nbsp;&nbsp; materials.&nbsp; It makes&nbsp; them&nbsp; very&nbsp; attractive&nbsp; and&nbsp; promising&nbsp; in&nbsp; the&nbsp; future&nbsp; in&nbsp; the&nbsp; treatment&nbsp; of&nbsp; river&nbsp; sediment contaminated with heavy metals.</p>

<p>Predmet izučavanja ove disertacije je ispitivanje mogućnosti primene homogenog, heterogenog i Fentonsličnog procesa u tretmanu obojenih otpadnih voda grafičke industrije.&nbsp; Kao Fenton katalizatori kori&scaron;ćeni su sintetisani gvožđe(III)-molibdat i nano nula valentno gvožđe, kao i komercijalni gvožđe(II)-sulfat. Istraživanja&nbsp; su sprovedena u četiri faze. U prvoj fazi&nbsp; je izvr&scaron;ena sinteza&nbsp; i karakterizacija&nbsp; Fenton&nbsp; katalizatora, pri čemu su ustanovljene njihove osnovne morfolo&scaron;ke karakteristike. Nano nula valentno gvožđe je sintetisano iz ekstrakta&nbsp; li&scaron;ća hrasta, dok je&nbsp; gvožđe(III)-molibdat sintetisan putem tzv. vlažnog hemijskog postupka. U drugoj fazi je&nbsp; izvr&scaron;ena optimizacija Fenton procesa u tretmanu sintetičkih rastvora grafičkih&nbsp; boja primenom nove statističke&nbsp; metode,&nbsp;<em> definitive screening design</em>.&nbsp; U&nbsp; cilju postizanja&nbsp; maksimalnog stepena obezbojavanja i mineralizacije tretiranog uzorka&nbsp; ispitan&nbsp; je&nbsp; uticaj&nbsp; sledećih&nbsp; procesnih parametara: inicijalne koncentracije boje, koncentracije gvožđa, pH vrednosti i koncentracije vodonik-peroksida. Nakon ustanovljenih optimalnih uslova i izvr&scaron;ene verifikacije predloženog optimuma, sproveden je tretman realnog efluenta.&nbsp; Stepen mineralizacije&nbsp; tretiranog&nbsp; efluenta&nbsp; ustanovljen&nbsp; je&nbsp; na&nbsp; osnovu&nbsp; vrednosti&nbsp; sadržaja&nbsp; ukupnog&nbsp; organskog&nbsp; ugljenika&nbsp; i&nbsp; hemijske&nbsp; potro&scaron;nje kiseonika.&nbsp; U cilju razumevanja mehanizma degradacije grafičkih boja u Fenton procesu, kao i identifikacije prirode&nbsp; degradacionih&nbsp; produkata,&nbsp; izvr&scaron;ena&nbsp; je&nbsp; kvalitativna&nbsp; gasno-hromatografska/maseno&nbsp; spektrometrijska analiza. Kinetika obezbojavanja realnog&nbsp; efluenta&nbsp; najbolje&nbsp; je opisana primenom&nbsp; Behnajady&nbsp; -&nbsp; Modirshahla&nbsp; -Ghanbary&nbsp; modela,&nbsp; koji&nbsp; defini&scaron;e&nbsp; inicijanu&nbsp; brzinu&nbsp; i&nbsp; oksidacioni&nbsp; kapacitet&nbsp; posmatranog&nbsp; procesa.&nbsp; Rezultati&nbsp; su ukazali&nbsp; na&nbsp; moguću&nbsp; primenu&nbsp; Fenton&nbsp; procesa&nbsp; u&nbsp; tretmanu&nbsp; CMYK&nbsp; boja&nbsp; usled&nbsp; postizanja&nbsp; visokih&nbsp; efikasnosti obezbojavanja i mineralizacije tretiranih efluenata. Nedostatak primenjene metode se ogleda u činjenici da je većina&nbsp; uzoraka&nbsp; okarakterisana&nbsp; kao&nbsp; visoko&nbsp; toksična,&nbsp; a&nbsp; ujedno&nbsp; i&nbsp; izrazito&nbsp; kisela,&nbsp; budući&nbsp; da&nbsp; je&nbsp; ustanovljena optimalna&nbsp; pH&nbsp; vrednost&nbsp; Fenton&nbsp; tretmana&nbsp; 2&nbsp; -&nbsp; 3.&nbsp; Stoga&nbsp; je&nbsp; u&nbsp; okviru&nbsp; treće&nbsp; faze&nbsp; istraživanja&nbsp; primenjen&nbsp; dodatni tretman&nbsp; realnog&nbsp; efluenta,&nbsp; adsorpcija&nbsp; na&nbsp; aktivnom&nbsp; uglju&nbsp; sintetisanom&nbsp; iz&nbsp; ko&scaron;tica&nbsp; divlje&nbsp; &scaron;ljive.&nbsp; Adsorpcioni tretman&nbsp; je rezultovao smanjenjem&nbsp; toksičnosti&nbsp; kod&nbsp; svih tretiranih uzoraka, koji&nbsp; se&nbsp; karakteri&scaron;u&nbsp; kao nisko do umereno toksični, te je sa tog aspekta moguće njihovo bezbedno ispu&scaron;tanje u recipijent. Ujedno je ustanovljena i povećana mineralizacija uzoraka, kao posledica degradacije jedinjenja koja su inicijalno doprinela povećanoj toksičnosti. U četvrtoj fazi rada primenjena je metoda ocenjivanja životnog ciklusa sinteze Fenton katalizatora. Rezultati LCA su utvrdili da sinteza heterogenog Fenton katalizatora, gvožđe(III)-molibdata, ostvaruje najveće opterećenje&nbsp; životne&nbsp; sredine,&nbsp; dok&nbsp; bi&nbsp; se&nbsp; proces&nbsp; sinteze&nbsp; nano&nbsp; nula&nbsp; valentnog&nbsp; gvožđa&nbsp; mogao&nbsp; unaprediti modifikovanjem ekstrakcione faze uz kori&scaron;ćenje alternativnih materijala i obnovljivih izvora energije. Značaj&nbsp; predstavljenih rezultata se ogleda u činjenici da su uzorci obojenih otpadnih voda grafičke industrije prvi put podvrgnuti Fenton tretmanu koji je rezultovao visokim stepenom efikasnosti.</p> / <p>The subject of this thesis is&nbsp; exploring the possibility of homogeneous, heterogeneous and Fenton-like process application in the treatment of dye wastewater in printing industry. Synthesized iron(III)-molybdate and nano zero valent iron, as well as commercial iron(II)-sulfate were used as a Fenton catalyst. The research was carried out in four&nbsp; phases.&nbsp; In&nbsp; the&nbsp; first&nbsp; phase,&nbsp; the&nbsp; catalyst&nbsp; synthesis&nbsp; and&nbsp; their&nbsp; characterization&nbsp; were&nbsp; performed,&nbsp; whereby&nbsp; the morphological characteristics were established. Nano zero valent iron was synthesized from&nbsp; oak leaf extract&nbsp; and iron(III)-molybdate was synthesized by wet chemical process. In the second phase, the optimization of Fenton process was performed within the treatment of synthetic printing dye solution using a new statistical method, a definitive screening design. In order to achieve maximum decolorization and mineralization of the treated sample, the influence of&nbsp; following&nbsp; process parameters was conducted: initial dye concentration, iron concentration, pH value&nbsp; and hydrogen peroxide concentration.&nbsp; The treatment of printing effluent was performed&nbsp; after&nbsp; establishing optimal&nbsp; conditions&nbsp; and&nbsp; verifying&nbsp; the&nbsp; proposed&nbsp; optimum&nbsp; values.&nbsp; Mineralization&nbsp; degree&nbsp; of&nbsp; treated&nbsp; effluent&nbsp; was determined based on the results of total organic carbon and chemical oxygen demand. In order to understand the dye&nbsp; degradation&nbsp; mechanism&nbsp; in&nbsp; Fenton&nbsp; process,&nbsp; as&nbsp; well&nbsp; as&nbsp; to&nbsp; identify&nbsp; degradation&nbsp; products,&nbsp; a&nbsp; qualitative&nbsp; gaschromatographic/mass spectrometric analysis was carried out. The&nbsp; kinetic studies of the printing effluent were best described by using the Behnajady- Modirshahla-Ghanbary model, which defines the initial speed and oxidation capacity of the process. The results indicated the possible application of the Fenton process in the treatment of CMYK dyes due to the high decolorization and mineralization efficiency of treated effluent. Disadvantage of the applied method is reflected in the fact that most of the samples are characterized as highly toxic and,&nbsp; at the same time, extremely acidic since the optimum pH value of Fenton treatment is 2 - 3. Therefore, in the third phase of the study, adsorption process on functionalized biochar prepared from wild plum kernels was applied on real printing effluent.&nbsp; Adsorption&nbsp; treatment&nbsp; resulted&nbsp; in&nbsp; toxicity&nbsp; reduction&nbsp; in&nbsp; all&nbsp; treated&nbsp; samples,&nbsp; characterized&nbsp; as&nbsp; low&nbsp; to moderately toxic. Therefore, from this aspect, treated effluent can be safely released into the recipient. At the same time, increased mineralization of the samples was established as a result of the compounds degradation that initially contributed to high toxicity. In the fourth phase, a life cycle assessment method of Fenton catalyst was applied. The results of the LCA indicated that the synthesis of the heterogeneous Fenton catalyst, iron(III) molybdate, achieved the highest environmental burden, while the synthesis of nano zero valent iron could be improved by modifying the extraction phase using alternative materials and renewable energy sources.&nbsp; The significance of the obtained results is high decolorization efficiency achieved by Fenton treatment of printing dye wastewater,&nbsp; which was used for the first time.</p>

Utilizing biomass such as lignin, bamboo, soybean, corn stalk, rice husk, etc., as a carbon source to produce graphene-based nanomaterials has been reported recently. However, the potential of using such nanomaterials for engineering and environmental applications has not been realized. This dissertation investigates the use of graphene-based nanomaterials synthesized from using biomass as a carbon source for water remediation and cement-based composites’ (CBCs) property enhancement. The first chapter introduces graphene and graphene-based nanomaterials, as well as the synthesis and application of graphene-based nanomaterials for removing heavy metals in an aqueous solution and for property enhancement in CBCs. The experimental investigation on the pyrolytic synthesis of graphene-encapsulated iron nanoparticles from biochar (BC) as the carbon source (BC-G@Fe0) was covered in the second chapter. Two synthetic routes for producing BC-G@Fe0, i.e., impregnation-carbonization (route-I) and pyrolysis-impregnation-carbonization (route-II) processes, were investigated experimentally using different characterization techniques and heavy metal removal methods. The third chapter reports the experimental performances of the heavy metal removal of Pb2+, Cu2+, and Ag+ from an aqueous solution using BC-G@Fe0. The effectivenesses of various adsorption benchmarks, such as pH, kinetics, and isotherms were assessed. Additionally, the removal efficiency of BC-G@Fe0 was evaluated. BC-G@Fe0 sample made from route II, in particular, FeCl2-impregnated-BC with 15% wt% iron loading carbonized at 1000 ℃ for 1h showed promising Pb2+, Cu2+, and Ag+ removal capacities of 0.30, 1.58, and 1.91 mmol/g, respectively. The fourth chapter experimentally investigated the reinforcement effect of commercially sourced, industrial graphene nanoplates (IG) on the mechanical properties of CBCs. This investigation was based on a hypothesis that the uniform dispersion of IG would significantly enhance the compressive strength of CBC. The main outcome of this research was that, while the wet dispersion mixing process of IG into CBC did not consistently yield significant increases in the composite compressive strength, but the newly proposed dry dispersion process demonstrated significant increases (22%) in the composite compressive strength. Chapter Five investigated the synthesis of lignin-based graphene nanoplatelets (LG) and their application in CBC reinforcement. The main findings were that LG did not show impressive increases compared to IG, even when dry dispersion was introduced. This was attributed to LG's lack of effective surface area compared to IG. Finally, a general conclusion and outlook for the future of research into biomass-based graphene nanomaterials were discussed in chapter six.

In the past 30 years zero-valent iron (ZVI) has become an increasingly popular reducing agent technology for remediating environmental contaminants prone to chemical degradation. Azo dyes and chlorinated organic compounds (COCs) are two classes of such contaminants, both of which include toxic compounds with known carcinogenic potential. ZVI has been successfully applied to the surfaces of permeable reactive barriers, as well as grown into nanoscale particles (nZVI) and applied in-situ to chemically reduce these contaminants into more environmentally benign compounds. However, the reactivity of ZVI and nZVI in these technologies is limited by their finite supply of electrons for facilitating chemical reduction, and the tendency of nZVI particles to homo-aggregate in solution and form colloids with reduced surface area to volume ratio, and thus reduced reactivity. The goal of this project was to combine reactive nanoparticle and membrane technologies to create an electro-catalytic permeable reactive barrier that overcomes the weaknesses of nZVI for the enhanced electrochemical filtration of azo dyes in solution. Specifically, nZVI was successfully grown and stabilized in a network of functionalized carbon nanotubes (CNTs) and deposited into an electrically conductive thin film on the surface of a polymeric microfiltration support membrane. Under a cathodic applied voltage, this thin film facilitated the direct reduction of the methyl orange (MO) azo dye in solution, and regenerated nZVI reactivity for enhanced electro-catalytic operation. The electro-catalytic performance of these nZVI-CNT membrane surface composites to remove MO was validated, modelled, and optimized in a batch system, as well as tested in a dead-end continuous flow cell system. In the batch experiments, systems with nZVI and a -2 V applied potential demonstrated synergistic enhancement of MO removal, which indicated the regeneration of nZVI reactivity and allowed for the complete removal of 0.25 mM MO batches within 2-3 hours. Partial least squares regression (PLSR) modelling was used to determine the impact of each experimental parameter in the batch system and provided the means for an optimization leading to maximized MO removal. Finally, tests in a continuous system yielded rates of MO removal 1.6 times greater than those of the batch system in a single pass, and demonstrated ~87% molar removal of MO at fluxes of approximately 422 lmh. The work herein lays the foundation for a promising technology that, if further developed, could be applied to remediate azo dyes and COCs in textile industry effluents and groundwater sites respectively. / Thesis / Master of Applied Science (MASc)

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