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The aim of the work was to assess the efficiency of ozonation and ozonation in combination with H$_2$O$_2$ in jet loop reactor to increase biotreatability of persistent veterinary antibiotic Tiamulin. The efficiency of oxidative processes was monitored by combined approach based on determination of efficiency of wastewater treatment and impact to waste sludge stabilization. Degradation of Tiamulin in model wastewater (100 mg L$^{−1}$) during oxidation was followed by COD and DOC measurements while changes in biodegradability were determined by respirometric measurements. Biogas production potential was also determined to identify problems related to anaerobic digestion of waste sludge resulted in treatment of Tiamulin-contaminated wastewater. At ozone dose of 69 g$_{ozone}$ g$_{COD}^{−1}$ and 220 g$_{ozone}$ g$_{DOC}^{−1}$removal for COD and DOC was 26% and 17%, respectively. Better biotreatability was confirmed by respirometric testing. H$_2$O$_2$ addition did not improve removal efficiency (11–13%). The second stage of nitrification was suppressed by the addition of Tiamulin and ozonation again recovered N-NO$^−_3$ formation. O$_3$/H$_2$O$_2$ treated sample reduced the nitrification, especially formation of N-NO$^−_2$ in the first phase of the process. Simultaneously, quadratic model was developed to describe the relationship between oxygen uptake rate and changes in ammonium nitrogen concentration due to the oxidative treatment. The positive impact of ozone was also confirmed by ozonation of Tiamulin-contaminated (400 mg L$^{−1}$) waste sludge where biogas production potential was increased for 6-times. Combination of approaches confirmed, that O$_3$ effectively increase the treatability of Tiamulin in wastewater and sludge while addition of the hydrogen peroxide generally did not improve the performance of the processes.

Aminoglikozidni antibiotik gentamicin sulfat v okolju predstavlja vedno večji problem, saj ga je nemogoče v celoti odstraniti iz odpadnih vod. Gentamicin sulfat je najbolj uporabljen antibiotik v skupini aminoglikozidnih antibiotikov in se uporablja za zdravljenje gram-negativnih okužb, izoliran pa je iz bakterije Micromonospora purpurea. Napredni oksidacijski procesi so najučinkovitejše nove metode, ki se uporabljajo za čiščenje in dezinfekcijo odpadnih vod, predvsem farmacevtskih ter za čiščenje biološko strupenih ali nerazgradljivih snovi. Osredotočili smo se na ozonacijo, saj velja za eno najuspešnejših metod čiščenja. V diplomski nalogi smo pod izbranimi pogoji ozonirali raztopino GS in učinkovitost procesa spremljali z določanjem kemijske potrebe po kisiku in koncentracije celotnega organskega ogljika. The aminoglycoside antibiotic gentamicin sulfate is an increasing problem in the environment, as it is impossible to completely remove it in wastewater. Gentamicin sulfate is the best antibiotic in the group of aminoglycoside antibiotics and is used to treat gram-negative infection and it’s isolated from bacteria Micromonospora purpurea. Advanced oxidation processes are the most effective new methods used for treatment and disinfection of wastewater, especially pharmaceuticals and for cleaning biologically toxic or non-degradable materials. We focused on ozonation, as it is considered one of the most successful treatment methods. In a degree thesis, we ozonated the GS solution under selected conditions and monitored the effectiveness of the process by determining chemical oxygen demand and concentration of total organic carbon.

Kakovost življenja se z razvojem tehnologije izboljšuje in k temu močno pripomore tudi farmacevtska industrija, ki razvija vedno več farmacevtskih učinkovin. S tem pa se tudi povečuje količina antibiotikov v okolju, predvsem v vodnem okolju. To predstavlja potencialno nevarnost za organizme, še posebej za razvoj bakterij, ki so odporne na antibiotike. Izkazalo se je, da za čiščenje odpadnih vod, v katerih se nahajajo antibiotiki, ne zadostujejo le konvencionalni postopki čiščenja. V ta namen se vedno pogosteje uporabljajo napredni oksidacijski postopki. V okviru magistrskega dela smo primerjali in optimizirali katalitske in nekatalitske tehnike ozonacije za odstranjevanje dveh izbranih antibiotikov iz odpadnih voda. Preučevali smo neposredno ozonacijo, posredno ozonacijo pri povišanem pH, posredno ozonacijo z dodatkom H2O2, katalitsko ozonacijo, foto-katalitsko ozonacijo, ozonacijo s Fentonovo oksidacijo in ozonacijo s foto-Fentonovo oksidacijo. Tekom raziskovalnega dela smo primerjali učinkovitosti razgradnje antibiotika amoksicilin in levofloksacin ter poskušali ugotoviti vpliv temperature na katalitske in nekatalitske procese ozonacije. Vse procese smo izvajali pri sobni (21 °C) in povišani (40 °C) temperaturi, da smo lahko določili temperaturno odvisnost kinetike procesa z določitvijo Arrheniusovih parametrov. Razgradnjo antibiotikov smo spremljali z določevanjem celotnega organskega ogljika (TOC) in kemijske potrebe po kisiku (KPK). Ugotovili smo, da pri vseh ozonacijah poteče dvostopenjska reakcija, kjer prva stopnja poteče hitreje in je v večini poskusov ozonacij bolj učinkovita v primerjavi z drugo stopnjo. Ob primerjavi učinkovitosti ozonacij glede na temperaturo se je v večini primerov izkazalo, da le-ta poteče hitreje pri povišani temperaturi v primerjavi s sobno temperaturo. Popolne mineralizacije ne moremo potrditi pri nobenem tipu ozonacije, saj učinkovitosti razgradnje antibiotika glede na TOC niso presegle 85 %. Glede na TOC in KPK rezultate lahko sklepamo, da je v večji meri potekla razgradnja antibiotika v stranske produkte. Na podlagi pridobljenih rezultatov lahko ugotovimo, da sta se za najbolj uspešna tipa ozonacij izkazala ozonacija s foto-Fentonovo oksidacijo ter posredna ozonacija pri povišanem pH in dodatkom H2O2. The quality of life is increasing with the development of new technologies. Pharmaceutical industry is very important in that regard as it makes large quantities of pharmaceutical products. On the other hand, concentrations of antibiotics are increasing in every environment especially in water ecosystems. This poses a great risk for organisms as well as it supports development of the antibiotic resistance genes in bacteria. It has been shown that conventional processes are not sufficient for treatment of wastewaters that contain antibiotics. That’s why there has been an increasing interest in advanced oxidation possesses for removing antibiotics form wastewaters. The aim of this research was to compare and optimise catalytic and non-catalytic ozonation for removal of two antibiotics from wastewaters. Direct ozonation, indirect ozonation at elevated pH, indirect ozonation with the edition of hydrogen peroxide, catalysed ozonation, photocatalytic ozonation, ozonation with Fenton oxidation and ozonation with photo-Fenton oxidation were compared for degradation of amoxicillin and levofloxacin. The effect of temperature dependence was also studied. All types of ozonation’s were carried out at room temperature (21°C) and at increased temperature (40°C). We consequently assessed the temperature dependence of kinetic process by calculating Arrhenius parameters. Degradation of antibiotics was monitored by measurement of total organic carbon (TOC) and chemical oxygen demand (COD). All types of ozonation proceeded in two stages. The first step was faster and more effective than the second one while comparing the efficiency at different temperatures. The degradation proceeded faster at higher temperatures. None of the samples was fully mineralised - TOC efficiency reached up to 85%. Based on TOC and COD results it can be concluded that the most effective types of ozonation are ozonation combined with photo-Fenton oxidation and direct ozonation at elevated pH with the addition of hydrogen peroxide.

Micropollutants and emerging substances pose a serious problem to environmental sustainability and remediation, due to their widespread use and applications in everyday life. This group of chemicals is diverse but with common toxic and harmful properties. Their concentration in the environment is often very low; however, due to their recalcitrant nature, they are persistent in air, water, and soil. From an engineering point of view, the challenge is not straightforward. It is difficult to remove these contaminants from complex mixtures of substances by conventional methods used in wastewater and drinking water treatment. Ozonation and ozone-based AOPs are accepted processes of degradation of resistant substances or at least enhancement of their biodegradability. The aim of this review paper is to present research trends aimed at solving problems in the research and application of ozone-based processes in the removal of micropollutants from wastewater, thus preventing leakage of harmful substances into surface water, soil, and groundwater and facilitating the reuse of wastewater. Priority substances, micropollutants and emerging pollutants, as well as processes and technologies for their transformation and elimination, are briefly specified. Results obtained by the authors in solving research projects that were aimed at eliminating selected micropollutants by ozonation and ozone-based AOPs are also presented. This review focuses on selected alkylphenols, petroleum substances, and organochlorine pesticides.

Naraščajoča uporaba antibiotikov in vse večja prisotnost farmacevtskih učinkovin v odpadnih vodah pomenijo vse resnejši okoljski problem. Ker se antibiotiki v telesu ne presnovijo popolnoma, jih večina konča v okolju, saj jih konvencionalne čistilne naprave niso zmožne popolnoma odstraniti. Poleg ljudi so pomemben vir onesnaženja tudi veterina, farmacevtska industrija, bolnišnice in raziskovalne dejavnosti. Antibiotiki se v okolju nahajajo v majhnih koncentracijah in zaradi svojega stalnega vnosa lahko negativno vplivajo tako na vodne organizme kakor tudi na ljudi. V okviru magistrskega dela sta predstavljena dva napredna oksidacijska procesa in njuna kombinacija za odstranjevanje antibiotika iz odpadnih vod. Antibiotik amoksicilin smo želeli odstraniti z ozonacijo, hidrodinamsko kavitacijo ter njuno kombinacijo. Postopke smo izvajali pri različnih pretokih ozona in različnih koncentracijah amoksicilina. Učinkovitost procesov smo spremljali z določanjem celotnega organskega ogljika (TOC) in kemijske potrebe po kisiku (KPK). Z respirometrijo aktivnega blata pa smo spremljali biorazgradljivost antibiotika. Rezultati so pokazali, da je sama ozonacija najučinkovitejši proces, saj smo dosegli največje učinkovitosti razgradnje – glede na TOC 26 % in glede na KPK 62 %. S hidrodinamsko kavitacijo nismo dosegli želenega učinka, saj so bile učinkovitosti najmanjše – glede na TOC < 1 %, glede na KPK pa 20 %. Kombinacija obeh postopkov pa je dala enake učinkovitosti kakor sam proces ozonacije. Z respirometrijo aktivnega blata smo dokazali, da neobdelan antibiotik tudi po kavitaciji ni biorazgradljiv. Le proces ozonacije in kombinaicija ozonacije ter kavitacije sta antibiotik vsaj delno razgradila in povečala njegovo biorazgradljivost. The increasing use of antibiotics and the presence of pharmaceutical residues in wastewater is becoming a serious environmental problem. Studies show that most of consumed antibiotics are not metabolized in the body. Conventional wastewater treatment plants are not able to completely remove them so they are constantly excreted into the environment. In addition to humans, an important source of antibiotics in effluents are also veterinary medicine, pharmaceutical industry, hospitals and research facilities. Antibiotics are found in low concentrations in the environment because of their continuous discharge they are a potential threat on aquatic organisms as well as humans. Within the master's thesis, two advanced oxidation processes and their combination for the removal of antibiotics from wastewater are presented. We studied ozonation, hydrodynamic cavitation and their combination. The processes were performed at different ozone flows and different concentrations of amoxicillin. The efficiency of the processes was monitored with determination of total organic carbon (TOC) and chemical oxygen demand (COD). Biodegradability of antibiotic was evaluated with respirometry of activated sludge. The results showed that ozonation itself is the most efficient process, as we achieved the highest decomposition efficiencies in terms of TOC 26 % and COD 62 %. Hydrodynamic cavitation did not achieve the preferred effect as the efficiencies were the lowest, according to the TOC < 1% and COD 20 %. The combination of both processes, however, gave the same results as the ozonation process itself. Respirometry of activated sludge proved that the untreated antibiotic is not biodegradable even after cavitation. Only the process of ozonation and the combination of ozonation and cavitation at least partially degraded the antibiotic, and increased its biodegradability.

Velika količina blata, ki nastane med biološkim čiščenjem odpadnih vod, predstavlja enega izmed glavnih problemov čistilnih naprav. Odlaganje oziroma ustrezna obdelava odpadnega aktivnega blata predstavlja do 65 % celotnih obratovalnih stroškov čistilne naprave. Ker odpadna voda predstavlja enega izmed glavnih virov antibiotikov v okolju, obstaja verjetnost, da se antibiotiki zaradi svoje kompleksne strukture v procesu biološkega čiščenja ne razgradijo popolnoma. Tako se lahko del antibiotikov v nespremenjeni obliki vrne nazaj v okolje, del pa se jih lahko adsorbira na odpadno aktivno blato, ki ga kasneje uporabimo kot substrat pri anaerobni obdelavi in produkciji bioplina. Antibiotiki v odpadnem aktivnem blatu inhibirajo produkcijo bioplina, saj svojim prisotnostjo omejijo aktivnost anaerobnih mikroorganizmov. Zato je potrebno odpadno aktivno blato pred vstopom v anaerobno obdelavo ustrezno obdelati. Pri anaerobni obdelavi kot stranska produkta nastaneta metan, ki predstavlja vir obnovljive energije in ogljikov dioksid. Med vsemi tehnikami naprednih oksidacijskih procesov se je ozonacija blata izkazala za uspešno metodo zmanjšanje inhibicije produkcije bioplina, ki je bila posledica onesnaženosti z antibiotiki. Ozon je močan oksidant, ki se veliko uporablja pri čiščenju odpadnih vod in obdelavi odpadnega aktivnega blata. Med obdelavo blata se ozon hitro pretvori v radikale in nastali radikali vplivajo na oksidacijo tako trdih delcev kot topnih organskih snovi. Med različnimi naprednimi oksidacijskimi procesi je obdelava z ozonom še posebej pomembna, ker po oksidaciji ni prisotnih oksidativnih ostankov, hkrati pa se koncentracija anorganskih soli ne poveča. V sklopu magistrskega dela smo preučili vpliv ozoniranja na učinkovitost anaerobne obdelave z antibiotiki kontaminiranega odpadnega aktivnega blata. Izvajali smo proces ozonacije aerobnega blata onesnaženega s tremi različnimi antibiotiki (tiamulinom, amoskicilinom in levofloksacinom). Ugotovili smo, da prisotnost katerega koli preiskovanega antibiotika povzroči inhibicijo produkcije bioplina, ki smo jo odpravili z 20 minutno ozonacijo kontaminiranega aerobnega blata. Po ozonaciji kontaminiranega aerobnega blata se je količina nastalega bioplina povečala od 20 do 36% v primerjavi s kontaminiranim aerobnim blatom. Prav tako se je povečal delež metana v bioplinu ozoniranega kontaminiranega aerobnega blata od 16 do 40 % v primerjavi z kontaminiranim aerobnim blatom. The large amount of sludge generated during biological wastewater treatment is one of the main problems of a biological treatment. Disposal or the appropriate treatment of waste activated sludge represents up to 65% of the total operating costs of the treatment plant. Wastewater is one of the main sources of antibiotics in the environment. Therefore, it is likely that antibiotics are not completely degraded in the biological treatment process due to their complex structure. Thus, some of the antibiotics can be returned unchanged to the environment, and some can be adsorbed to waste activated sludge, which is later used as a substrate in anaerobic digestion and biogas production. Antibiotics in waste activated sludge inhibit biogas production by limiting the activity of anaerobic microorganisms. Consequently, waste activated sludge needs to be properly processed before entering anaerobic digestion. Anaerobic digestion produces by-products methane, which is a source of renewable energy, and carbon dioxide. Among all advanced oxidation process techniques, sludge ozonation has shown to be a successful method for the reduction of the inhibition of biogas production due to antibiotic contamination. Ozone is a powerful oxidant that is widely used in wastewater treatment and waste activated sludge treatment. During sludge treatment, ozone is rapidly converted into radicals, which affect the oxidation of both solid particles and soluble organic matter. Among the various advanced oxidation process techniques, ozone treatment is particularly important because no oxidative residues are present after oxidation, and at the same time, the inorganic salts concentration does not increase. As part of the master's thesis, we examined the effect of ozonation on the effectiveness of anaerobic treatment with antibiotics of contaminated waste activated sludge. We performed the process of ozonation of aerobic sludge contaminated with three different antibiotics (tiamulin, amoxicillin and levofloxacin). We found that the presence of any model antibiotic caused inhibition of biogas production, which was eliminated by 20 minutes of ozonation of contaminated aerobic sludge. After ozonation of contaminated aerobic sludge, the amount of biogas produced increased from 20% to 36% compared to contaminated aerobic sludge. The proportion of methane in the biogas of ozonated contaminated aerobic sludge also increased from 16% to 40% compared to the sample of contaminated aerobic sludge.

Anaerobna razgradnja je učinkovita metoda odstranjevanja onesnaževal iz odpadnih vod in ena izmed najpogosteje uporabljenih metod stabilizacije odvečnega blata bioloških čistilnih naprav. Mikroorganizmi razgradijo organske snovi pri anaerobnih pogojih, kjer sta prevladujoča produkta razgradnje metan (CH4) in ogljikov dioksid (CO2), torej bioplin, ki ga lahko izrabimo v energetske namene. Aktivno blato iz čistilne naprave in živalsko blato sta se izkazala za problematična substrata, saj vsebujeta nepredelane antibiotične učinkovine ali produkte njihove razgradnje. Antibiotiki in druge kemijske spojine lahko zavirajo delovanje mikroorganizmov, ki sodelujejo pri procesu anaerobne razgradnje in tako zmanjšajo produkcijo bioplina, torej energetsko izrabo odpadnega materiala. S poskusom določanja anaerobne razgradljivosti smo želeli določiti učinkovitost ozonacije za predobdelavo aerobnega blata, kontaminiranega s tremi različnimi antibiotiki (amoksicilin, tiamulin in levofloksacin). Ozonacija je ena izmed naprednih oksidacijskih procesov, s katerim lahko kompleksne organske molekule razgradimo v manjše in lažje razgradljive molekule. Namen raziskave je ugotoviti, če lahko z ozonacijo kontaminiranega aerobnega blata odpravimo zaviralne učinke antibiotikov na anaerobne mikroorganizme in obenem pridobimo zadostno količino bioplina. Ugotovili smo, da vsi trije antibiotiki v aerobnem blatu negativno vplivajo na anaerobno razgradnjo. Rezultati so pokazali, da ozonacija aerobnega blata prispeva k večji produkciji bioplina med njegovo obdelavo v anaerobnih pogojih, večjemu deležu CH4 v bioplinu in odpravi zaviralni učinek antibiotikov. Ob dodatku amoksicilina oz. tiamulina je prišlo do 20 % inhibicije produkcije bioplina, medtem ko je ob dodatku levofloksacina prišlo do 26 % inhibicije. Ozonacija je pri vseh treh vzorcih, kontaminiranih z antibiotiki, odpravila zaviralne učinke. V primerjavi z neozoniranim kontaminiranim aerobnim blatom se je količina bioplina po ozonaciji vzorca z amoksicilinom povečala za 74 %, pri vzorcu s tiamulinom za 69 % in pri vzorcu z levofloksacinom za 55 %. Prav tako smo ugotovili, da ozonacija aerobnega blata in kontaminiranega aerobnega blata poveča delež CH4 v bioplinu. V primerjavi z neozoniranim kontaminiranim aerobnim blatom se je delež CH4 po ozonaciji pri amoksicilinu povečal za 12 %, pri tiamulinu za 14 %, pri levofloksacinu pa za 18 %. Anaerobic digestion is an effective method of removing pollutants from wastewaters and one of the most frequently used methods for the stabilization of redundant biological treatment plant’s activated sludge. Microorganisms digest organic matter under the anaerobic conditions, producing mostly methane (CH4) and carbon dioxide (CO2) as by-products, named biogas, which can be used as an energy source. Activated sludge from the wastewater treatment plant and animal manure have proved to be problematic substrates, since they contain antibiotic substances and products of their degradation. Antibiotics and other chemical compounds can inhibit the activity of microorganisms involved in the process of anaerobic digestion and thus decrease the biogas production, consequently reducing the energy recovery from waste material. In this study, anaerobic digestion experiment was performed to determine the ozonation efficiency for the pre-treatment of anaerobic waste, contaminated with three different antibiotics (amoxicillin, tiamulin and levofloxacin). Ozonation is one of the advanced oxidation processes, which can break down complex organic molecules into smaller and more easily degradable molecules. The purpose of the thesis is to find out, if ozonation of contaminated aerobic sludge can be used to eliminate the inhibitory effects of antibiotics on anaerobic microorganisms and to assure the production of sufficient amounts of biogas. All three antibiotics had negative impact on the anaerobic digestion. The results showed that ozonation contributes to an increased production of biogas during anaerobic digestion, to an increased rate of CH4 in the biogas and eliminates the inhibitory effect of antibiotics. The addition of amoxicillin or tiamulin inhibited the biogas production by 20 %, while the addition of levofloxacin inhibited it by 26 %. In all three samples, contaminated with antibiotics, the ozonation eliminated the inhibitory effects. Compared to the non-ozonated contaminated aerobic sludge, the amount of biogas increased by 74 % after ozonation of the sample with amoxicillin, in the case of the sample with tiamulin by 69 % and in the case of the sample with levofloxacin by 55 %. We also found that ozonation increases the percentage of CH4 in the biogas. Compared to the non-ozonated contaminated active sludge, the percentage of CH4 after the ozonation increased by 12 % in the case of amoxicillin, by 14 % in the case of tiamulin and by 18 % in the case of levofloxacin.

Razširjena uporaba antibiotikov je povzročila, da se njihov obseg v okolju dnevno globalno povečuje. Antibiotiki se v telesu ne presnovijo v celoti. Večina antibiotikov se v okolje vnese preko živali, saj se v veterini uporabljajo kot zdravstvena preventiva, za zdravljenje bakterijskih okužb, z namenom pospeševanja rasti in/ali prirasta živali, preostanek pa v okolje vnesemo ljudje, zaradi zdravljenja bakterijskih okužb. Vnos antibiotikov v okolje neposredno najbolj vpliva na vodne organizme, predvsem pa je vse bolj skrb vzbujajoč pojav odpornih bakterij oz. superbakterij. Te bakterije so odporne proti antibiotikom in posledično nanje antibiotiki ne delujejo več, zato je vse več še pred kratkim preprosto ozdravljivih bakterijskih okužb težje ozdravljivih oz. neozdravljivih. Odstranjevanje antibiotikov je torej nujno. Zaradi vstopa večine antibiotikov v vodno okolje, se osredotočamo predvsem na odstranjevanje iz odpadnih vod. Konvencionalne komunalne čistilne naprave antibiotikov niso sposobne odstraniti in posledično lahko ti preprosto vstopijo v površinske vode, podtalnico in tudi pitno vodo. Za odstranjevanje antibiotikov iz odpadnih vod se vse bolj uporabljajo napredni oksidacijski procesi. Namen magistrske naloge je bil primerjava različnih naprednih oksidacijskih procesov za čiščenje odpadnih vod, ki vsebujejo antibiotike in preveritev, ali so ti postopki primerni za odstranjevanje antibiotikov iz vodnega okolja. Preučevali smo naslednje tehnike oz. postopke: direktna ozonacija, ozonacija pri povišanem pH (pH=9,5), ozonacija pri povišanem pH (pH=9,5) ob dodatku H2O2, ozonacija, katalizirana z dodatkom Fe2+, ozonacija, katalizirana z dodatkom Fe2+ in UV svetlobe, ozonacija s Fentonovo oksidacijo in ozonacija s foto-Fentonovo oksidacijo. Učinkovitost tehnik smo ovrednotili s spremljanjem celotnega organskega ogljika (TOC) in kemijske potrebe po kisiku (KPK). Ugotovili smo, da pri vseh postopkih proces poteče dvostopenjsko z bolj učinkovito prvo stopnjo procesa. Direktna ozonacija se je izkazala za najmanj učinkovito od vseh preučevanih postopkov, tako glede na TOC, kot KPK rezultate. Učinkovitost ozonacije se je povečala ob povišanem pH, ob dodatku UV, H2O2 in/ali katalizatorjev. Najučinkovitejša je bila ozonacija s foto-Fentonovo oksidacijo, s katero smo dosegli med 83 in 96 % stopnjo oksidacije prisotnih antibiotikov, ter med 65 in 84 % stopnjo mineralizacije, torej popolno razgradnjo antibiotikov v anorganske komponente, CO2 in H2O. S tem smo potrdili, da so napredni oksidacijski procesi primerni postopki za odstranjevanje antibiotikov iz odpadnih vod. The widespread use of antibiotics has been causing increase of their extent in the environment. Antibiotics are not completely metabolised in the body. Most antibiotics come into the environment through animals, as they are used in the veterinary medicine for health prevention, for the treatment of bacterial infections, with the purpose to promote growth and/or animal increment. The rest come to the environment because of human consumption, due to the treatment of bacterial infections. Antibiotics into the environment directly affect the aquatic organisms, and above all, the increasing concern arouses phenomenon of resistant bacteria or superbacteria. These bacteria are resistant to antibiotics and, consequently, they are not affected by them, so nowadays more and more bacterial infections are more difficult to be cured or are even incurable. Therefore, the removal of antibiotics is necessary. Due to the entry of most antibiotics in the aquatic environment, their removal from wastewater is the most important. Conventional municipal wastewater treatment plants are not capable of removing antibiotics and thus they can easily enter surface water, groundwater, and even drinking water. The main focus nowadays is the addition of the tertiary cleaning using advanced oxidation processes. The purpose of this thesis was to compare the various advanced oxidation processes for wastewater treatment containing antibiotics and verification if these procedures are suitable for the removal of antibiotics from the aquatic environment. We studied the following experimental techniques/procedures: direct ozonation, ozonation at elevated pH (pH = 9.5), ozonation at elevated pH (pH = 9.5) at the addition of H2O2, catalysed ozonation by addition of Fe2+, catalysed ozonation by addition of Fe2+ and UV light, ozonation with Fenton oxidation and ozonation with photo-Fenton oxidation. The methods were evaluated according to the total organic carbon (TOC) and chemical oxygen demand (COD). It can be concluded that studied procedures occur in two phases with first stage of process to be more effective. Direct ozonation was the least effective in terms of TOC, as well as COD. The efficiency of the ozonation increased at elevated pH, with the addition of UV, H2O2 and/or catalysts. The most effective procedure was ozonation with photo-Fenton oxidation, where we achieved between 83 and 96% oxidation of the present antibiotics and between 65 and 84% mineralization, hence the complete decomposition of antibiotics into inorganic components, CO2, and H2O. Our results confirmed that advanced oxidation processes are appropriate for removing antibiotics from wastewater.

Obstaja veliko kompleksov kovin prehoda, ki se velikokrat uporabljajo v katalizi, zato je aktualna tudi priprava novih vrst kompleksov. Del teh so tudi kleščasti PNP, PCP in CNC kompleksi s kovinami. Kompleksi različnih kovin se zelo razlikujejo po stabilnosti, zato je njihova priprava in uporaba od tega zelo odvisna. Ker imajo kovine v teh kompleksih različna oksidacijska stanja, je od tega odvisno tudi kateri ligandi in koliko se jih veže na kovino. Med vsemi temi kompleksi so zelo zanimivi za raziskave hidridni kompleksi kovin prehoda, predvsem monodentatni hidridni kompleksi, oziroma monohidridni kompleksi. Pri teh kompleksih je načeloma na voljo samo eno mesto, kjer lahko poteče reakcija, zato lahko bolje kontroliramo reakcijo. Poznanih je relativno malo takšnih kompleksov kovin prehoda, predvsem iridijevih in rodijevih. V magistrski nalogi sem naredila delni pregled literaturnih podatkov o hidridnih kompleksih kovin prehoda in pripravila ter preučevala reakcije oksidacije Au(I) monohidridnih kompleksov s kisikom in ozonom. There are many transition metal complexes which are often used in catalysis, so the preparation of new types of complexes is also important. These include pincer PNP, PCP and CNC complexes with metals. Complexes of different metals differ greatly in their stability, so their preparation and use are highly dependent on this. Since the metals in these complexes have different oxidation states, it also depends on which ligands and how strongly they bind to the metal. Among all these complexes, the hydride complexes of transition metals are of great interest to researchers, especially the monodentate hydride complexes or monohydride complexes. In these complexes, there is basically only one site where the reaction can occur, so we can better control the reaction. Relatively few such transition metal complexes are known, mainly iridium and rhodium ones. In my master's thesis, I did a partial literature survey of transition metal hydride complexes and prepared and studied the oxidation reactions of Au(I) monohydride complexes with oxygen and ozone.

Advanced oxidation processes (AOPs) have been introduced to deal with different types of water pollution. They cause effective chemical destruction of pollutants, yet leading to a mixture of transformation by-products, rather than complete mineralization. Therefore, the aim of our study was to understand complex degradation processes induced by different AOPs from chemical and ecotoxicological point of view. Phenol, 2,4-dichlorophenol, and pentachlorophenol were used as model pollutants since they are still common industrial chemicals and thus encountered in the aquatic environment. A comprehensive study of efficiency of several AOPs was undertaken by using instrumental analyses along with ecotoxicological assessment. Four approaches were compared: ozonation, photocatalytic oxidation with immobilized nitrogen-doped TiO2 thin films, the sequence of both, as well as electrooxidation on boron-doped diamond (BDD) and mixed metal oxide (MMO) anodes. The monitored parameters were: removal of target phenols, dechlorination, transformation products, and ecotoxicological impact. Therefore, HPLC–DAD, GC–MS, UHPLC–MS/MS, ion chromatography, and 48 h inhibition tests on Daphnia magna were applied. In addition, pH and total organic carbon (TOC) were measured. Results show that ozonation provides by far the most suitable pattern of degradation accompanied by rapid detoxification. In contrast, photocatalysis was found to be slow and mild, marked by the accumulation of aromatic products. Preozonation reinforces the photocatalytic process. Regarding the electrooxidations, BDD is more effective than MMO, while the degradation pattern and transformation products formed depend on supporting electrolyte.

Napredni oksidacijski procesi so metode oksidacije, pri katerih dobimo zelo močan oksidant hidroksilni radikal (•OH). Ti procesi se uporabljajo predvsem za oksidacijo organskih onesnaževal, ki se v procesu lahko popolnoma mineralizirajo do ogljikovega dioksida, vode in anorganskih spojin. Kadar mineralizacija ni popolna, dobimo oksidacijske medprodukte, ki so lahko bolj strupeni od začetne organske molekule, zato moramo preveriti tudi njihov vpliv na okolje. V diplomskem delu smo se osredotočili predvsem na študijo sprememb strupenosti pri ozonaciji odpadne vode. Kot modelno odpadno vodo smo uporabili raztopino tiamulin fumarata s koncentracijo 400 mg/L. Raztopino smo ozonirali v štirih ciklih šaržne ozonacije. Vsak cikel je trajal 10 minut. Spremembo strupenosti antibiotika med oksidacijo smo ugotavljali z ekotoksikološkimi testi z malo vodno lečo Lemna minor. Poleg strupenosti smo analizirali še spremembo celotnega organskega ogljika med ozonacijo. Rezultati so pokazali, da raztopina timaulin fumarata in ozonirani vzorci te raztopine zavirajo rast male vodne leče ter zmanjšujejo koncentracijo klorofila v členkih rastline. Strupenost raztopine se po ozonaciji ni spremenila, saj so razlike specifičnih rasti členkov male vodne leče vseh ozoniranih vzorcev napram začetni raztopini antibiotika zelo majhne. Kljub temu, da se je koncentracija celotnega organskega ogljika med ozonacijo zmanjšala, pa se strupenost ni spremenila, kar nakazuje na prisotnost medproduktov, ki so prav tako strupeni. Advanced oxidation processes are methods of oxidation, in which a very strong oxidazing agent, hydroxyl radical, is generated. They are mainly used for the oxidation of organic pollutants, which can be completly mineralized to carbon dioxide, water and inorganic compounds. When mineralization is incomplete, oxidation by-products are obtained and may be even more toxic than the initial organic molecule. Their impact on the environment needs to be assessed. The aim of this diploma thesis was to study the toxicity of ozonated wastewater. A solution of the antibiotic, tiamulin fumarate, in a concentration 400 mg/L was used as the model wastewater. The solution was treated with four ozonation cycles in a batch reactor. Each cycle lasted 10 minutes. The effects of antibiotic were determined by ecotoxicological tests on duckweed Lemna minor. In addition to toxicity testing, we also analysed the content of total organic carbon during ozonation. The results of the experiment have shown that the solution of timulin fumarate and the ozonated samples of this solution inhibit the growth of a Lemna minor and reduce the concentration of chlorophyll in fronds of the plant. The toxicity of the solution did not change after ozonation, as the differences in the specific growth of all of the ozonated samples compared to the initial antibiotic solution are very small. Despite the fact that the total organic carbon decreased during ozonation, the toxicity did not change, indicating the presence of toxic by-products.

Ostanki antibiotikov in drugih zdravil, postajajo vse resnejši problem, saj jih najdemo v izpustih iz farmacevtskih in proizvodnih obratov, bolnišnic in odplakah iz čistilnih naprav. Različne študije so pokazale, da so ostanki antibiotikov prisotni v odpadnih in površinskih vodah, zadnje študije pa kažejo trend zviševanja tudi v tleh, podtalnici ter pitni vodi. Čeprav so izmerjene koncetracije v širokem koncentracijskem območju od ng/L do µg/L, so lahko nekateri razgradni produkti aktivnih snovi celo bolj toksični kot izvorna snov. Predhodne študije so pokazale, da so najvišje koncentracije antibiotikov v bolnišničnih odpadnih vodah. Za odstranitev takšnih onesnaževal pa obstoječe čistilne naprave niso primerne, saj velike količine antibiotikov ostajajo v vodi tudi po čiščenju. V doktorski disertaciji so predstavljeni trije procesi odstranjevanja teh onesnaževal iz bolnišničnih odpadnih vod. Glavni namen je bil poiskati napredne, izvedljive metode za odstranitev izbranih antibiotikov iz bolnišnične odpadne vode. V prvem delu smo se osredotočili na postopek čiščenja s sub in super-kritično oksidacijo, kjer smo preučili procesne parametre: vpliv temperature, tlaka, pretoka in časa. V drugem delu smo opravili postopek ozonacije, kjer smo spremljali učinkovitost čiščenja odpadne vode s spreminjanjem pH vzorca, različnimi odmerki ozona ter dodatek vodikovega peroksida (H2O2). V tretjem delu smo za čiščenje sintetično pripravljene bolnišnične odpadne vode uporabi aerobni reaktor, kjer smo iskali optimalen bivalni čas. Vsebnost antibiotikov smo po vsaki metodi čiščenja določali z optimiranimi LC-MS/MS analiznimi tehnikami. V zadnjem delu doktorske disertacije smo vse omenjene postopke čiščenja implementirali na realnem vzorcu bolnišnične odpadne vode. Vsebnost antibiotika v realnem vzorcu pred in po čiščenju smo določali z ekstrakcijo na trdni fazi v povezavi z optimirano LC-MS/MS tehniko. Na koncu smo izvedli še test inhibicije porabe kisika z aktivnim blatom za oksidacijo ogljika in amonija, s katerim smo poskušali ugotoviti, toksičen vpliv očiščene vode na mikrooganizme v aktivnem blatu. The residues of antibiotics and other medicines are becoming an increasingly serious problem because they can be found in discharges from pharmaceutical and manufacturing plant, hospitals and sewage from treatment plants. Various studies showed that antibiotic residues are present in wastewaters and surface waters, and recent studies show an increase in ground water, drinking water and in the soil. Although the measured concentrations are in a wide range from ng/l to µg/l, some degradation products of the active substances may be even more toxic than the parent substance. Preliminary studies have shown that the highest concentrations of antibiotics are found in hospital wastewater. In order to remove such pollutants, existing treatment plants are not suitable, as large amounts of antibiotics remain in the water after cleaning. The doctoral dissertation presents three processes for removing these pollutants from hospital wastewater. The main purpose was to find advanced, feasible methods for the removal of selected antibiotics from hospital wastewater. In the first part, we focused on the process of purification with sub and super-critical oxidation, where we examined the process parameters: the influence of temperature, pressure, flow and time. In the second part, we carried out the ozonation process, where we monitored the efficiency of wastewater treatment by changing the pH of the sample, the different ozone doses, and the addition of hydrogen peroxide (H2O2). In the third part, the aerobic reactor was used to clean synthetically prepared hospital wastewater, where we were looking for an optimal residence time. The antibiotic content was determined after each purification method with optimized LC-MS/MS analytical techniques. In the last part of the doctoral dissertation, all the mentioned cleaning procedures were implemented on a realistic sample of hospital wastewater. The antibiotic content in the real sample before and after purification was determined by solid phase extraction in conjunction with the optimized LC-MS/MS technique. Finally, an oxygen consumption test with an activated sludge for the oxidation of carbon and ammonia was carried out, with which we attempted to determine the toxic effect of purified water on microorganisms in the active mud.

Porast količine farmaceutika u okolišu posljedica je naglog razvoja u medicini i farmaciji te njihove intenzivnije primjene. Okolišni vodeni sustavi najizloženija su okolišna sastavnica onečišćenju farmaceuticima. Farmaceutici u vodeni okoliš dospijevaju otpadnim vodama iz postrojenja farmaceutske industrije, nepravilnim odlaganjem neiskorištenih lijekova na odlagalištima te preko komunalnih otpadnih voda kao nemetabolizirane farmaceutske tvari i/ili metaboliti nastali ulaskom aktivne farmaceutske tvari u razne biološke reakcije u organizmu. Nastali metaboliti problem su za sebe, jer često znaju biti manje pogodnih svojstava po okoliš od početne farmaceutske tvari, na primjer toksičniji te teže ili ne biorazgradivi. Salicilna kiselina (SA) glavni je metabolit acetilsalicilne kiseline, poznatije po trgovačkom nazivu aspirin. SA također je prirodno prisutna u nekim biljkama kao fitohormon te se koristi u liječenju raznih kožnih bolesti. Proces ozonacije pokazao se kao učinkovit način njezinog uklanjanja iz otpadnih i okolišnih voda. Istražena je učinkovitost referentnog procesa direktne ozonacije, procesa ozonacije kao naprednog oksidacijskog procesa, katalitičke ozonacije (O3/Fe2+, O3/Mn2+), ozonacije pod UV-C zračenjem (UV-C/O3) te katalitičke ozonacije u kombinaciji s UV-C zračenjem (UV-C/Fe2+/O3 i UV-C/Mn2+/O3) za mineralizaciju SA-e pri dvije različite pH vrijednosti (pH 3 i 11). Prema dobivenim rezultatima NPOC analize, znatno ubrzanje mineralizacije ostvareno je katalitičkim procesima, uz i bez djelovanja UV zračenja, u usporedni s direktnom i naprednom ozonacijom. Katalitički proces UV-C/Fe2+/O3 predstavlja proces s najvećom brzinom mineralizacije, a može se opisati kinetičkim modelom nultoga reda, pri čemu je kobs = 74,3 M^-1 min^-1. Zatim su ispitane promjene okolišnih pokazatelja (KPK, BPK5 i akutna toksičnost na Vibrio fischeri) tijekom obrade vode opterećene SA-om, anorganskim solima (kloridima, nitratima, fosfatima i sulfatima) te NOM-om za referentni proces direktne ozonacije i UV-C/Fe2+/O3 proces. Najznačajniji porast biorazgradivosti kod direktne ozonacije ostvaren je u prisutnosti klorida te NOM-a, dok procesom UV-C/Fe2+/O3 dolazi do male, neznatne porasti biorazgradivosti svih ispitivanih matrica. Vidljiva je smanjena toksičnost po V. fischeri pri svim eksperimentima direktne ozonacije, a u svim istraživanim slučajevima nakon provedbe UV-C/Fe2+/O3 procesa otopine su pokazale stimulirajući učinak prema V. fischeri. The increase in the amount of pharmaceuticals in the environment is the result of rapid development of medicine and pharmacy, and also the more intensive use of pharmaceuticals. Environmental water systems are the most exposed to contamination with pharmaceuticals. Pharmaceuticals enter the environment via pharmaceutical industry plants, via improper disposal of unused pharmaceutics on landfills, and as metabolites and/or non-metabolised pharmaceutical supstances that are the result of various biological reactions of active pharmaceutical ingredients (API) in the organisms via municipal waste water. The resulting metabolites that are formed this way are a problem for themselves, as they often have less favorable environmental properties than the initial matter, for example they are more toxic and harder or non-biodegradable. Salicylic acid (SA) is the major metabolite of acetylsalicylic acid, known by the commercial name aspirin. SA is also naturally present in some plants as phytohormone, and it is used in the treatment of various skin diseases. Ozonation proved to be an effective way of removing SA from waste and natural water. In this paper the effectiveness of the reference process of direct ozonation, the ozonation as an advanced oxidation process, catalytic ozonation (O3/Fe2+, O3/Mn2+), UV-C ozonation (UV-C/O3) and catalytic ozonation combined with UV-C radiation (UV-C/Fe2+/O3 i UV-C/Mn2+/O3) for mineralization of SA at two different pH values (pH 3 and pH 11) was investigate. According to the results of the NPOC analysis, in comparison with direct and advanced ozonation, a significant acceleration of mineralization was achieved by catalytic processes with and without UV radiation. The catalytic process of UV-C/Fe2+/O3 represents the process with the highest rate of mineralization and it can be described by the zero-order kinetic model with kobs = 74,3 M^-1 min^-1. Subsequently, changes in environmental parameters (COD, BOD5 and acute toxicity on Vibrio fischeri) were monitored in direct ozonation and UV-C/Fe2+/O3 treatment of water loaded with SA, inorganic salts (chlorides, nitrates, phosphates and sulphates) and NOM. The most significant increase of biodegradability in direct ozonation treatment was achieved in the presence of chloride and NOM, while the UV-C/Fe2+/O3 process results in a small, slight increase in biodegradability in all tested matrices. There was a significant decrease in toxicity on V. fischeri in all experiments with direct ozonation experiments, and in all investigated cases with applied UV-C/Fe2+/O3 process, the solutions showed a stimulating effect towards V. fischeri.

Odvečno blato predstavlja veliko finančno breme, saj strošek odstranjevanja blata na čistilnih napravah predstavlja kar 50% do 60% celotne finančne porabe. V današnjem svetu poznamo in uporabljamo več različnih načinov in procesov, ki potrjeno zmanjšujejo odvečno blato nastalo med procesom čiščenja odpadnih voda. Eden izmed teh procesov je ozonacija. Za namene primerjave v raziskovalnem delu, se je najprej ozoniralo samo blato, nato se je postopek ozonacije integriral v proces čiščenja odpadne vode s šaržnim biološkim reaktorjem (SBR). Za ovrednotenje procesa smo analizirali parametre KPK, TN, TP, NO3--N in NH4+-N, z analizo sušin in žarin pa se je določila koncentracija blata in koncentracija hlapne snovi v blatu za oceno uspešnosti odstranjevanja blata. S samo ozonacijo smo uspeli doseči znižanje koncentracije blata za 60,7% pri dozi 80 g ozona/kg suhe snovi. Koncentracije KPK, TN in TP v supernatantu so se z višjo dozo ozona pričakovano povišale, saj slednji poškoduje celično steno celic v blatu, to pa povzroči da se znotrajcelične snovi razpustijo v supernatant. Točko preloma smo določili pri dozi 30 g ozona / kg suhe snovi, zaradi najvišjega skoka KPK ter sorazmerno nizkega in obvladljivega povečanja koncentracij TN in TP. Pri integraciji ozonacije v proces čiščenja odpadne vode smo dosegli 83% znižanje količine odvečnega blata, pri povprečni dozi 11,1 g ozona/kg suhe snovi blata. KPK, TN, TP, NO3-N in NH4-N so bili pri čiščenju odpadne vode na iztoku pod mejno vrednostjo za izpust. Največji problem je predstavljal TN zaradi velikega vpliva ozonacije na denitrifikacijo. Poraba energije za ozonacijo je znašala 453 kW h na tono dehidriranega blata, kar, po naših izračunih, znese 46,95 € po toni. Excess sludge represents a major financial burden, because the cost of disposal of sludge at wastewater treatment plants can represent up to 50 % – 60 % of the total financial expenditure. Nowadays we use several certified methods and processes to reduce excess sludge generated during the process of wastewater treatment. One of these processes is ozonation. For the purpose of comparison in the research work, excess sludge was firstly ozonated in batch, then the process of ozonation was integrated in the process of wastewater treatment using a sequencing batch reactor (SBR). COD, TN, TP, NO3--N and NH4+-N were analyzed to evaluate process efficiency. Total and volatile solids concentrations were used to determine the concentration of the sludge and the efficiency of sludge degradation. With batch ozonation, we have achieved a 60.7 % reduction in the concentration of sludge with a dose of 80 g of ozone/kg of dry matter. The concentrations of COD, TN and TP in the supernatant were expectedly increased with higher doses of ozone, since they damage the sludge cell walls and this causes the intracellular substances to dissolve in the supernatant. The optimum point was determined at a dose of 30 g of ozone/kg of dry matter, due to the maximum increase of COD and relatively low and manageable increase in the concentrations of TN and TP. With the integration of ozonation into the SBR process of wastewater treatment, 83% of excess sludge degradation was achived, at an average dose of ozone of 11.1 g/kg total solids. In the wastewater effluent, COD, TN, TP, NO3-N and NH4-N concentrations were under the limit values for release into the environment. The largest problem represented TN concentration, because of a high impact of ozonation on denitrification. The energy consumption for ozonation was 453 kWh per tonne of dehydrated sludge, which according to our calculations amounts to 46,95 € per tonne.

Farmaceutici imaju pozitivan učinak na ljude i životinje, ali problemi mogu nastati njihovim dospijećem u okoliš. Jedan od najčešće detektiranih farmaceutika u vodenim sustavima je diklofenak. Glavni put njegova dospijevanja u okoliš su efluenti uređaja za obradu komunalnih otpadnih voda, zbog nemogućnosti uklanjanja tog tipa onečišćivala konvencionalnim postupcima obrade. Za uklanjanje diklofenaka i njemu sličnih spojeva iz vode učinkovitima su se pokazali napredni oksidacijski procesi među kojima se ističu fotokatalitički procesi zbog svoje ekološke i ekonomske prihvatljivosti. U ovom radu provedena je imobilizacija TiO2 fotokatalizatora na stakleni nosač koji je korišten za razgradnju diklofenaka u vodenom mediju UV-A/TiO2 procesom uz vodikov peroksid. Istraživana je učinkovitost regeneracije fotokatalizatora kemijskom metodom ozonacije. Aktivnost regeneriranog imobiliziranog sloja TiO2 testirana je u ponovljenim fotokatalitičkim ciklusima. Zamijećen je pad aktivnosti fotokatalizatora neovisno o uvijetima provedbe procesa regeneracije ozonacijom. Pharmaceuticals have benefit for human and animal health but the problem is identified when traces of pharmaceutical are found in natural environment. One of the most commonly detected pharmaceuticals in natural water is diclofenac. Main pathways of diclofenac entering water environment are wastewater treatment plant effluents, due to its inefficient removal by conventional wastewater treatment methods. Advanced oxidation processes are found to be efficient for diclofenac removal from water, among them photocatalytic processes are distinguished due to their ecological and economic advantages. I this research TiO2 photocatalyst was immobilized on the glass plates which were used for diclofenac degradation in water applying UV-A/TiO2 process with hydrogen peroxide. Efficiency of the chemical regeneration by ozonation of photocatalyst was investigated. Activity of regenerated photocatalyst was tested by reuse for the diclofenac removal. Decrease of the photocatalyst activity was noticed regardless the conditions of the regeneration process.

Podzemne vode Panonskog bazena predstavljaju složen sustav s kompleksnom strukturom kontaminanata s visokim koncentracijama teških metala i arsena, visokom obojenošću i mutnoćom, visokim koncentracijama suspendiranih tvari, amonija i drugih hranjivih soli te visokim organskim opterećenjem. Uzroci smanjene kvalitete podzemne vode mogu se podijeliti na prirodne i antropogene. S obzirom na kompleksnost sastava podzemne vode, potrebno je primijeniti kombinirani pristup obrade voda da bi se udovoljilo nacionalnim propisima te smjernicama Svjetske zdravstvene organizacije. U ovoj doktorskoj disertaciji razvijena je nova metoda i sustav pročišćavanja podzemne vode koji jamči istodobno uklanjanje širokog spektra zagađivala i visoku kvalitetu pročišćene vode s obzirom na sve mjerene parametre, a neovisan je o temperaturnim promjenama i o ulaznom opterećenju. U tu svrhu korištena je kombinacija elektrokemijskih metoda (elektrokoagulacija, elektroredukcija, elektrooksidacija) i naprednih oksidacijskih procesa (UV+ozon), (UV+H2O2). Uzorci podzemnih voda uzeti su s područja istočne Slavonije u Osječko-baranjskoj županiji, na lokaciji Darde te u Vukovarsko-srijemskoj županiji na lokacijama Andrijaševaca, Antina, Komletinaca i Vrbanje (Hrvatska). Uzorci voda iz Vojvodine uzeti su s područja vodocrpilišta Zrenjanina i Temerina (Srbija). Uzorci voda iz Arizone uzeti su sa 6 lokacija na području grada Camerona/Tuba Cityja (SAD). Laboratorijskim (“jar”) testovima optimizirani su parametri kao što su: materijal elektroda, broj elektroda, ukupna površina reaktorskih elektroda za svaku vrstu materijala, razmak elektroda, jakost struje, trajanje procesa. Cilj je bio postići optimalan odnos stupnja pročišćavanja, utrošene energije i vremena aplikacije, te istodobno generirati što manju količinu otpadnog mulja. Dokazane su prednosti elektrokemijske obrade u odnosu na postojeće metode fizičko-kemijske obrade. Na osnovu dobivenih parametara konstruirano je pilot-postrojenje kapaciteta 1 m3/dan na kojemu je bila provjerena učinkovitost razvijene metode. Na osnovu dobivenih rezultata i provedene optimizacije radnih parametara procesa osigurana je tehnološka baza za konstrukciju i proizvodnju nove generacije industrijskih uređaja za pročišćavanje pitkih voda. Uz neznatne prilagodbe metodu je moguće primjeniti i za obradu različitih tipova industrijskih efluenata. Dobivena saznanja iskorištena su konkretno kod konstrukcije industrijskog uređaja za pročišćavanje procjednih voda kapaciteta 10 m3/dan, instaliranog na odlagalištu „Viševac“ kod Rijeke. Groundwater of Pannonian Basin presents a complex system with a complex mixture of contaminants with high concentrations of heavy metals and arsenic, highly staining and turbidity, high concentrations of suspended solids, ammonia and other nutrients, and high organic load. The causes of reduced quality of groundwater can be divided into natural and anthropogenic. Considering the complex structure of groundwater it is necessary to apply a combined approach of water treatment in order to satisfy both national regulations and guidelines of the World Health Organization. In this doctoral thesis, a new method and system of purification of groundwater is developed that guarantees the simultaneous removal of wide range of contaminants and high quality of purified water considering all measured parameters, and is independent of temperature changes and input load. For this purpose a combination of electrochemical methods (electrocoagulation, electroreduction, electrooxidation) and advanced oxidation processes (UV+ozone), (UV+H2O2) was used. Groundwater samples were taken in the area of Eastern Slavonia in Osijek-Baranja County on location in Darda, and in Vukovar-Srijem County in locations Andrijaševci, Antin, Komletinci and Vrbanja (Croatia). Samples of water were taken in Vojvodina in the area of cities Zrenjanin and Temerin (Serbia). Samples of water were taken in Arizona on six locations in the city of Cameron/Tuba (USA). By the laboratory (“jar”) tests the parameters were optimized such as the material of electrodes, number of electrodes, the overall surface of the reaction plates for each type of material, electrode distance, electric current, duration of the process. The aim was to achieve an optimal ratio of purification, energy and application time, and at the same time generate an even smaller amount of sludge. On the basis of these obtained parameters the pilot plant capacity of 1 m3/day was constructed and the effictiveness of the developed method was proven. Based on the obtained results and performed process optimization of the working parameters, the technology base for the design and fabrication of a new generation of industrial units for purification of drinking water was provided. With someminor adjustments, the method can be applied for the treatment of various types of industrial effluents. The resulting findings are used specifically for the construction of the industrial leachate treatment plant capacity of 10 m3 / day, installed at the landfill "Viševac" near Rijeka.

Podzemne vode Panonskog bazena predstavljaju složen sustav s kompleksnom strukturom kontaminanata s visokim koncentracijama teških metala i arsena, visokom obojenošću i mutnoćom, visokim koncentracijama suspendiranih tvari, amonija i drugih hranjivih soli te visokim organskim opterećenjem. Uzroci smanjene kvalitete podzemne vode mogu se podijeliti na prirodne i antropogene. S obzirom na kompleksnost sastava podzemne vode, potrebno je primijeniti kombinirani pristup obrade voda da bi se udovoljilo nacionalnim propisima te smjernicama Svjetske zdravstvene organizacije. U ovoj doktorskoj disertaciji razvijena je nova metoda i sustav pročišćavanja podzemne vode koji jamči istodobno uklanjanje širokog spektra zagađivala i visoku kvalitetu pročišćene vode s obzirom na sve mjerene parametre, a neovisan je o temperaturnim promjenama i o ulaznom opterećenju. U tu svrhu korištena je kombinacija elektrokemijskih metoda (elektrokoagulacija, elektroredukcija, elektrooksidacija) i naprednih oksidacijskih procesa (UV+ozon), (UV+H2O2). Uzorci podzemnih voda uzeti su s područja istočne Slavonije u Osječko-baranjskoj županiji, na lokaciji Darde te u Vukovarsko-srijemskoj županiji na lokacijama Andrijaševaca, Antina, Komletinaca i Vrbanje (Hrvatska). Uzorci voda iz Vojvodine uzeti su s područja vodocrpilišta Zrenjanina i Temerina (Srbija). Uzorci voda iz Arizone uzeti su sa 6 lokacija na području grada Camerona/Tuba Cityja (SAD). Laboratorijskim (“jar”) testovima optimizirani su parametri kao što su: materijal elektroda, broj elektroda, ukupna površina reaktorskih elektroda za svaku vrstu materijala, razmak elektroda, jakost struje, trajanje procesa. Cilj je bio postići optimalan odnos stupnja pročišćavanja, utrošene energije i vremena aplikacije, te istodobno generirati što manju količinu otpadnog mulja. Dokazane su prednosti elektrokemijske obrade u odnosu na postojeće metode fizičko-kemijske obrade. Na osnovu dobivenih parametara konstruirano je pilot-postrojenje kapaciteta 1 m3/dan na kojemu je bila provjerena učinkovitost razvijene metode. Na osnovu dobivenih rezultata i provedene optimizacije radnih parametara procesa osigurana je tehnološka baza za konstrukciju i proizvodnju nove generacije industrijskih uređaja za pročišćavanje pitkih voda. Uz neznatne prilagodbe metodu je moguće primjeniti i za obradu različitih tipova industrijskih efluenata. Dobivena saznanja iskorištena su konkretno kod konstrukcije industrijskog uređaja za pročišćavanje procjednih voda kapaciteta 10 m3/dan, instaliranog na odlagalištu „Viševac“ kod Rijeke., Groundwater of Pannonian Basin presents a complex system with a complex mixture of contaminants with high concentrations of heavy metals and arsenic, highly staining and turbidity, high concentrations of suspended solids, ammonia and other nutrients, and high organic load. The causes of reduced quality of groundwater can be divided into natural and anthropogenic. Considering the complex structure of groundwater it is necessary to apply a combined approach of water treatment in order to satisfy both national regulations and guidelines of the World Health Organization. In this doctoral thesis, a new method and system of purification of groundwater is developed that guarantees the simultaneous removal of wide range of contaminants and high quality of purified water considering all measured parameters, and is independent of temperature changes and input load. For this purpose a combination of electrochemical methods (electrocoagulation, electroreduction, electrooxidation) and advanced oxidation processes (UV+ozone), (UV+H2O2) was used. Groundwater samples were taken in the area of Eastern Slavonia in Osijek-Baranja County on location in Darda, and in Vukovar-Srijem County in locations Andrijaševci, Antin, Komletinci and Vrbanja (Croatia). Samples of water were taken in Vojvodina in the area of cities Zrenjanin and Temerin (Serbia). Samples of water were taken in Arizona on six locations in the city of Cameron/Tuba (USA). By the laboratory (“jar”) tests the parameters were optimized such as the material of electrodes, number of electrodes, the overall surface of the reaction plates for each type of material, electrode distance, electric current, duration of the process. The aim was to achieve an optimal ratio of purification, energy and application time, and at the same time generate an even smaller amount of sludge. On the basis of these obtained parameters the pilot plant capacity of 1 m3/day was constructed and the effictiveness of the developed method was proven. Based on the obtained results and performed process optimization of the working parameters, the technology base for the design and fabrication of a new generation of industrial units for purification of drinking water was provided. With someminor adjustments, the method can be applied for the treatment of various types of industrial effluents. The resulting findings are used specifically for the construction of the industrial leachate treatment plant capacity of 10 m3 / day, installed at the landfill "Viševac" near Rijeka.

Tijekom proteklih petnaest godina, farmaceutici dobivaju sve više pozornosti kao potencijalne bioaktivne kemikalije u okolišu. Smatraju se opasnim zagađivačima jer njihove dozvoljene propisane količine još nisu regulirane i nisu postavljeni zakonodavni okviri za te vrijednosti. Farmaceutici se konstantno ispuštaju u okoliš i prisutni su u vrlo malim koncentracijama koje mogu utjecati na kvalitetu vode za piće, ekosustav i zdravlje ljudi.

Oksidacija ozonom je danas sve popularnija u raznim postrojenjima za obradu pitkih i otpadnih voda, zbog njegove izvanredne oksidacijske moći. Međutim povezano je s ozonacijom neizbježno nastajanje raznih kemijskih sporednih produkata, radi čega je potrebno razumjeti prirodu tih spojeva, te njihovu stabilnost i potencijalan utjecaj na zdravlje. U ovom je radu razvijena jednostavna metoda analize formaldehida, kao najvažnijeg i najbrojnijeg sporednog produkta ozonacije, na tekućinskom kromatografu visoke djelotvornosti sa UV/VIS detektorom. Metoda je osnovana na EPA standardnoj metodi 8315A i temelji se na kvantitativnoj derivatizaciji aldehida 2, 4-dinitrofenilhidrazinom i kromatografskom određivanju derivata. Separacija je provođena mobilnom fazom 70:30 acetonitril:voda, u vremenu od 10 minuta (uz povećanje vremena analize metoda se može upotrijebiti i za druge aldehide) i uz temperaturu kolone od 200 °C. Pokazana je mogućnost uklanjanja formaldehida na biofiltru s ispunom od kvarcnoga pijeska, aktiviranog nakon odgovarajućeg perioda prilagodbe mikroorganizama za tu zadaću. Nadalje, formaldehid se učinkovito uklanja i pri pročišćavanju otpadnih voda aktivnim muljem.

Osnovni princip membranske separacije je da se pomoću membrana određene poroznosti odvajaju molekule filtrirane tekućine u dvije frakcije: koncentrat (retentat) i permeat. Otopljene tvari, čestice i organske tvari ne mogu proći kroz membranu već se odvode u odvod kao koncentrat ili otpadna voda. Otpadna vode zbog sadržaja različitih soli i organskih spojeva čija je prisutnost u okolišu nepoželjna ne može se ispustiti u okoliš bez prethodne odgovarajuće obrade. U radu je vršena obrada NF koncentrata valpovačke vode primjenom procesa koagulacije/flokulacije pomoću vapna i natrij hidroksida u cilju smanjenja koncentracije soli te ponovnog vraćanja vode u proces, postignuta je učinkovitost uklanjanja soli karbonatne tvrdoće od 83-98 %. Postupkom flokulacije/koagulacije organske tvari ne uklanjaju se u dovoljnoj mjeri pa se postupak pokušao pospješiti naprednim oksidacijskim procesima kao što je ozonacija i Fentonov proces. Rezultati dobiveni ozonacijom pokazuju da je najintenzivnije uklanjanje TOC-a od 46, 5 % postignuto nakon 150 min ozonacije. Nakon obrade Fentonovim procesom također su izmjerene zadovoljavajuće vrijednosti pokazatelja kvalitete vode. Postignuto je uklanjanje TOC-a od 51, 77 %, i smanjenje vrijednosti permanganatnog broja ispod 5 O2 mgL-1 što zadovoljava zakonske propise.