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Oljkarstvo je v Sredozemlju izredno razvito in kot vsaka kmetijska panoga se spopada z različnimi boleznimi ter paraziti, ki napadajo rastline. Najbolj razširjen škodljivec je oljčna muha (Bactrocera oleae), ki so jo tradicionalno zatirali z dimetoatom. V diplomskem delu sem pregledala literaturo o vplivu dimetoata na okolje in na netarčne organizme v kopenskem in vodnem ekosistemu. Dimetoat je organofosfatni insekticid in deluje predvsem na acetilholin esterazo, ki je eden izmed najpomembnejših živčnih encimov. Zaradi izpostavljenosti temu pesticidu se spremeni aktivnost še nekaterih drugih encimov, kot so na primer karboksilaza, aspartatamino transferaza in alanin transaminaza. Dimetoat vpliva tudi na rast in razmnoževanje številnih organizmov, pri višjih koncentracijah povzroča celo smrt. Zaradi teh negativnih posledic na okolje je bil dimetoat prepovedan v Evropski uniji. Posledično so se v oljkarstvu razvile alternativne metode boja proti oljčni muhi. Nekatere izmed teh še vedno predvidevajo uporabo manj strupenih organofosfatnih insekticidov, ki vseeno negativno učinkujejo na okolje. Zato je pomembno, da se razvija druge metode, ki minimalno vplivajo na okolje. Olive-growing and olive oil production are in the Mediterranean area particularly important. Every agricultural discipline has its own problems with pests and infections. In olive-growing is the main pest the olive fruit fly (Bactrocera oleae). Traditionally the farmers used an organophosphorus insecticide dimethoate. In this diploma thesis, the effects of dimethoate on the environment and on non-target organisms that are living in the aquatic and terrestrial ecosystems are presented. Dimethoate affects the cholinergic nervous system, especially the enzyme acetylcholinesterase. It also affects the activity of different enzymes as carboxylase, aspartate aminotransferase, alanine transaminase. Dimethoate affects growth, reproduction and cause even death. Because of these negative effects European commission banned dimethoate in 2019. There are other methods that can be used against the olive fruit fly. Some of them uses insecticides, even organophosphates, which are less harmful than dimethoate, but still toxic for non-target organisms. New methods need to be developed with minimal impact on the environment.

U okviru doktorske disertacije razvijena je metoda za kvantitativno određivanje ostataka 27 nesteroidnih protuupalnih lijekova, kemijski različitih spojeva, tekućinskom kromatografijom ultra visoke djelotvornosti povezane s masenom spektrometrijom u uzorcima hrane životinjskog podrijetla (mlijeku, mišićnom tkivu) i uzorcima vode iz okoliša (otpadna voda). Optimiziran postupak ekstrakcije iz složenih matrica temelji se na enzimskoj hidrolizi koju slijedi ekstrakcija acetonitrilom, a dobiveni ekstrakt je pročišćen, uz istovremeno koncentriranje, ekstrakcijom na čvrstoj fazi. Validacijom metode ispitane su zadane značajke učinkovitosti koje su zadovoljile zakonski postavljene kriterije prihvatljivosti. Istraživanje je obuhvatilo i analizu realnih uzoraka s područja Republike Hrvatske, 449 uzoraka hrane životinjskog podrijetla i 96 uzoraka otpadnih voda. Kako bi se dobile informacije o toksičnosti tih spojeva koji dospijevaju u okoliš, in vitro testom na staničnim linijama ribe i ljudi ispitan je njihov citotoksični učinak. In this dissertation, a method for the quantitative determination of 27 nonsteroidal anti-inflammatory drug residues by ultra high performance liquid chromatography – mass spectrometry in food of animal origin (milk, muscle) and environmental water (wastewater) was developed. Optimised sample processing consisted of enzymatic hydrolysis and acetonitrile extraction was followed by a clean-up of the extract by solid phase extraction. By validation of the method, verified performance characteristics complied with the legally set acceptability criteria. The study also included the analysis of the real samples from regions of the Republic of Croatia, 449 samples of food of animal origin and 96 samples of wastewater. In order to obtain information on the toxicity of these compounds that are released into the environment, their cytotoxic effect was examined using in vitro test on fish and human cell lines.

Current standardized laboratory test protocols use model species that have limitations to accurately assess native species responses to stressors. We developed and tested a novel acute insitu protocol for testing field-collected organisms. We used Asellus aquaticus and NaCl as a reference toxicant to test for the effects of location (laboratory vs. insitu), medium (synthetic vs. field water), substrate (presence vs. absence), and protocol replicability. We further tested the protocol using groundwater-adapted isopods: Proasellus assaforensis for the effect of location, P. cavaticus of medium and P.lusitanicus of substrate. Our results showed that A.aquaticus’ lethality obtained with the novel acute insitu protocol did not significantly differ from those from laboratory testing. However, laboratory tested P.assaforensis showed a higher sensitivity, suggesting that its acclimation to laboratory conditions might have pernicious effects. A. aquaticus and P. cavaticus showed a higher mortality using synthetic medium insitu and under laboratory conditions, which overestimated the stressor’s effect. Besides, substrate use had no significant effect. The novel acute insitu protocol allows the use of native species under realistic scenarios. It is particularly well adapted for assessing the risk of groundwater ecosystems but it can be applied to a wide range of ecosystems.

Plastika ima v industriji pomembno vlogo, zato se njena proizvodnja iz leta v leto povečuje. Pomanjkanje učinkovitih metod za odstranjevanje plastike po uporabi se odraža v čedalje večjem onesnaženju naravnih okolij, kjer zaradi vpliva okoljskih dejavnikov počasi razpada in tako predstavlja glavni vir onesnaženja ekosistemov z mikroplastiko. Organizmi, ki so mikroplastiki izpostavljeni bi lahko imeli povečano tveganje za razvoj bolezenskih stanj. Mikroplastika lahko povzroča fizične poškodbe tkiv prebavne in dihalne poti. Služi lahko tudi kot vektor za prenos ostalih toksičnih onesnažil, ki se iz okolja akumulirajo na njeni površini. Pogosto mikroplastika vsebuje tudi nevarne aditive, ki so ji dodani ob izdelavi. Z analizami proteoma lahko identificiramo tarče toksičnega delovanja na molekularni ravni, vendar pa je takšnih raziskav na področju posledic izpostavljenosti mikroplastiki do danes še zelo malo. V raziskovalni nalogi smo proučevali vpliv mikroplastike na proteom modelne praživali Tetrahymena thermophila. Za ločevanje in identifikacijo proteinov, katerih raven se je ob izpostavitvi glede na kontrolno skupino spremenila, smo uporabili tehniko dvo-dimenzionalne poliakrilamid gelske elektroforeze (2-D PAGE), ki smo jo združili z masno spektrometrijo. Identificirali smo 4 proteine, katerih vsebnost je bila pri izpostavljenih kulturah signifikantno spremenjena glede na kontrolno skupino in ugotovili, da lahko preko slednjih mikroplastika vpliva na številne metabolne procese, kot so transkripcija, regulacija celičnega cikla, segregacija kromosomov, translacija, popravne mehanizme DNA, proces apoptoze in razgradnjo proteinov pri testnem organizmu Tetrahymena thermophila. Plastics represents an important material in modern world and its production is growing every year. The lack of efficient methods for its disposal after is resulting in increasing contamination of the environment where it is subjected to slow degradation under constant changes of the environmental factors. This process results in the production of the most microplastics found in the environment. Organisms that are subjected to microplastic particles may have increased risk for developing health problems, caused by physical damaging of the digestive or respiratory tract tissues. In addition, other toxic chemicals that are present in the environment can accumulate on the surface of the particles which can serve as a vector for their transmission. Microplastics also often contains dangerous additives that are added during the production. Proteome analysis is an important tool for identification of the molecular targets of pollutants. However, very few studies have so far been published on the effects of microplastics at the molecular, especially proteome level. In this research two-dimensional polyacrylamide gel electrophoresis (2-D PAGE), coupled with mass spectrometry was used to identify the effects of microplastics exposure on Tetrahymena thermophila proteome. Four differentially expressed proteins were identified after exposing the model organism Tetrahymena thermophila to polyethylen beads. The results revealed that microplastics can affect different metabolic pathways such as transcription, cell cycle regulation, chromosomal segregation, translation, DNA repair mechanisms, apoptosis and protein degradation.

Mūsdienās ar vides piesārņojumu saistītie izaicinājumi kļūst arvien nozīmīgāki. Nepietiekama notekūdeņu attīrīšana un to piesārņojums var atstāt negatīvas sekas uz vidi un apdraudēt dažādus dzīvos organismus. Bakalaura darba mērķis ir izpētīt un salīdzināt attīrītu un neattīrītu notekūdeņu ietekmi uz Daphnia magna dzīvotspēju, balstoties uz ISO ekotoksikoloģiskā testa (6341:2013) standarta metodiku. Attīrītu un neattīrītu notekūdeņu paraugi tika ievākti četru pilsētu notekūdeņu attīrīšanas iekārtās: Aizputē, Dobelē, Liepājā un Saldū. Darba pētnieciskā daļa – salīdzināt attīrītu un neattīrītu notekūdeņu ietkekmi uz Daphnia magna– tika veikta Daugavpils Universitātes aģentūras “Latvijas Hidroekoloģijas institūtā” Voleru ielā 4, Rīgā. Ekotoksikoloģijas testi tika veikti 2021. gada rudenī un ziemā. Bakalaura darba temats: Attīrītu un neattīrītu municipālo notekūdeņu ietekme uz Daphnia magna dzīvotspēju. Bakalaura darba galvenie rezultāti: Daphnia magna dzīvotspēja ievērojami pasliktinās neattīrīto municipālo notekūdeņu klātbūtnē. Lai noskaidrotu ūdens kvalitāti visvairāk ietekmējošos faktorus pirms un pēc attīrīšanas, ir nepieciešama tālāka izpēte. Atslēgas vārdi: Notekūdeņi, D. magna, dzīvotspēja, ekotoksikoloģija., Nowadays, the challenges of environmental pollution are becoming increasingly important. Insufficient treatment and pollution of wastewater can have negative consequences for the environment and endanger various living organisms. The bachelor’s thesis aims to study and compare the effect of treated and untreated wastewaters on the viability of Daphnia magna, based on the standard methodology of the ISO ecotoxicological test (6341:2013). Samples of treated and untreated wastewater were collected at wastewater treatment plants in four cities: Aizpute, Dobele, Liepaja and Saldus. The research part of the work – to compare the effect of treated and untreated wastewater on Daphnia magna – was performed at the Latvian Institute of Aquatic Ecology, Voleru street 4, Riga. The research was conducted in the autumn and winter of 2021. Title of thesis: Effects of treated and untreated municipal wastewaters on the viability of Daphnia magna. The most important results: Viability of Daphnia magna is significantly impaired in the presence of untreated municipal wastewaters. Further research is needed to ascertain the most damaging factors for water quality before and after standard treatment. Keywords: wastewater, D. magna, viability, ecotoxicity.

Atmosferske lebdeće čestice (engl. particulate matter, PM) spadaju među najznačajnije polutante u okolišu. Prema aerodinamičkom promjeru se dijele na grube (da

Plastmasas piesārņojums mūsdienās ir aktuāla problēma un tā negatīvā ietekme ir novērojama ūdens vidē. Plastmasas daļiņas, sadaloties par mikroplastmasu, negatīvi ietekmē ūdens organismus, mazinot to dzīves ilgumu un kvalitāti. Darbā tika apskatīta sintētiskā auduma un krāsvielu ekotoksikoloģiskā, un bioķīmiskā ietekme uz sānpeldēm Hyalella azteca un Pontogammarus robustoides. Rezultāti liecina par plastmasas daļiņu un krāsvielu negatīvu hronisku ietekmi uz H. azteca reprodukciju, konstatējot embriju deformāciju vai neattīstīšanos. Biomarķieri CAT un GST norādīja uz oksidatīvo stresu plastmasas daļiņu ietekmē. Kā arī biomarķieris AChE norādīja uz neirotoksisku iedarbību plastmasas daļiņu ietekmē. Līdzīga sintētiskā auduma akūta ietekme tika konstatēta P. robustoides, norādot uz izdzīvotības samazināšanos un paaugstinātu oksidatīvo stresu plastmasas klātbūtnē., Plastic pollution has become an important problem nowadays and its negative effects are visible in the aquatic environment. Plastic particles, when broken down into microplastics, have a negative effect on aquatic organisms and reduce their lifespan and quality. In this thesis the ecotoxicological and biochemical effects of synthetic fabric and dyes on the amphipods Hyalella azteca and Pontogammarus robustoides were examined. The results indicate an adverse long-term effect of plastic particles and dyes on the reproduction of H. azteca by detecting deformation or underdevelopment of the embryos. The biomarkers CAT and GST indicated oxidative stress in the amphipods under the influence of plastic particles. The biomarker AChE also indicated neurotoxic effects from plastic particles. A similar acute effect of plastic particles was observed in P. robustoides, indicating a decrease in survival and increased oxidative stress in the presence of plastic.

Secondary salinization of freshwater is becoming a growing environmental problem. Currently, there is few data available on the effects of salinisation on subterranean crustaceans that are vital for the maintenance of groundwater ecosystem functioning. In this study, the sensitivity of subterranean Niphargus amphipods to NaCl was investigated. We expected that cave-dwelling species would be more sensitive as surface-subterranean boundary species. Eight ecologically different Niphargus species were tested: four live at the boundary between the surface and subterranean ecosystems (N. timavi, N. krameri, N. sphagnicolus, N. spinulifemur), three live in cave streams (N. stygius, N. scopicauda, N. podpecanus), and one species (N. hebereri) lives in anchialine caves and wells. The organisms were exposed to five concentrations of NaCl for 96 h and afterwards the immobility, mortality, and electron transfer system (ETS) activity (a measure for metabolic rate of animals) were evaluated. As expected, the most tolerant species was N. hebereri dwelling in naturally high-salinity habitat. However, contrary to our expectations, the species collected at the surface-subterranean boundary were more sensitive as cave stream species when their immobility and mortality were assessed. Interestingly, the majority of Niphargus tested were more NaCl tolerant as can be deduced from currently available data for subterranean and surface crustaceans. We could not observe a clear trend in ETS activity changes between groups of surface-subterranean boundary and cave streams species after exposure to NaCl stress, but it appears that osmotic stress-induced metabolic rate changes are species-specific. This study shows that amphipods Niphargus can be a valuable subterranean environmental research model and further ecotoxicity research is of interest.

Current farm systems rely on the use of Plant Protection Products (PPP) to secure high productivity and control threats to the quality of the crops. However, PPP use may have considerable impacts on human health and the environment. A study protocol is presented aiming to determine the occurrence and levels of PPP residues in plants (crops), animals (livestock), humans and other non-target species (ecosystem representatives) for exposure modelling and impact assessment. To achieve this, we designed a cross-sectional study to compare conventional and organic farm systems across Europe. Environmental and biological samples were/are being/will be collected during the 2021 growing season, at 10 case study sites in Europe covering a range of climate zones and crops. An additional study site in Argentina will inform the impact of PPP use on growing soybean which is an important European protein-source in animal feed. We will study the impact of PPP mixtures using an integrated risk assessment methodology. The fate of PPP in environmental media (soil, water and air) and in the homes of farmers will be monitored. This will be complemented by biomonitoring to estimate PPP uptake by humans and farm animals (cow, goat, sheep and chicken), and by collection of samples from non-target species (earthworms, fish, aquatic and terrestrial macroinvertebrates, bats, and farm cats). We will use data on PPP residues in environmental and biological matrices to estimate exposures by modelling. These exposure estimates together with health and toxicity data will be used to predict the impact of PPP use on environment, plant, animal and human health. The outcome of this study will then be integrated with socio-economic information leading to an overall assessment used to identify transition pathways towards more sustainable plant protection and inform decision makers, practitioners and other stakeholders regarding farming practices and land use policy.

The increasing use of substances with endocrine disruptive properties (EDs) not only impacts aquatic organisms but can also have a direct negative effect on human health. In this comprehensive worldwide review, we collected ecotoxicology and concentration data observed in surface water for 53 high-potency EDs and performed a risk assessment. The compounds were selected from the EU watchlist of priority substances, expanded with new compounds of emerging concern (total 41), where quantifiable data were available for the past three years (2018-2020). The risk quotients ranged from

U disertaciji je razvijen novi računalni postupak procjene ekotoksikološkog rizika vodenih staništa uzrokovan bioaktivnim kemijskim onečišćivalima sastavljen od tri cjeline: utvrđivanja stanja, određivanja rizika od postojećim metodama, te razvoja i primjene novih QSAR modela za procjenu rizika. Utvrđeno je da su vodena staništa rijeke Save opterećena kemijskim onečišćivalima od rastućeg značaja za okoliš. S obzirom na nedostatke postojećih QSAR metoda za procjenu rizika razvijenih na malom broju spojeva, novi robusniji QSAR modeli razvijeni su na nekoliko tisuća kemikalija iz baza ToxCast i Tox21 s brojnim i osjetljivijim toksičnim učincima izmjerenim na staničnim linijama i embrijima zebrice. Novi modeli temeljeni su na molekularnim deskriptorima i strukturnim otiscima, a dobiveni su logističkom regresijom, neuronskim mrežama i slučajnim šumama koje su dale ponajbolje modele. Dobiveni modeli pokazuju dobru generalizaciju na vanjskim skupovima onečišćivala, a njihova kvaliteta provjerena je novouvedenim metrikama. Procjene ekotoksikološkog rizika od spojeva utvrđenih u rijeci Savi temeljena na novim modelima toksičnosti pokazuju dobro slaganje s postojećim metodama, uz značajno povećanje kemijskog strukturnog prostora kojeg pokrivaju. A novel computational approach for assessing the ecotoxicological risk for water habitats caused by bioactive chemical pollutants is developed in this work. It consists of three parts: the determination of current ectoxicological status, the risk assessment based on existing methods, and the development and application of new QSAR models for risk assessment. Water habitats of the Sava River were found to be burdened with chemical pollutants of growing importance to the environment. Given the shortcomings of existing QSAR risk assessment methods developed on a small number of compounds, new, more robust QSAR models were developed herein on several thousand chemical compounds from the ToxCast and Tox21 databases which were assessed on more sensitive toxic endpoints measured on zebrafish embryos and cell lines. The newly developed models are based on molecular descriptors and structural fingerprints and are obtained by logistic regression, neural networks and random forests which gave the best models. The trained models show good generalization on external sets of chemical compounds. Their quality is validated by newly introduced metrics. Ecotoxicological risk assessment of compounds identified in the Sava River, is based on the new toxicity models which agree well with the existing methods, supported by a significant increase of structural space covered.

U disertaciji je razvijen novi računalni postupak procjene ekotoksikološkog rizika vodenih staništa uzrokovan bioaktivnim kemijskim onečišćivalima sastavljen od tri cjeline: utvrđivanja stanja, određivanja rizika od postojećim metodama, te razvoja i primjene novih QSAR modela za procjenu rizika. Utvrđeno je da su vodena staništa rijeke Save opterećena kemijskim onečišćivalima od rastućeg značaja za okoliš. S obzirom na nedostatke postojećih QSAR metoda za procjenu rizika razvijenih na malom broju spojeva, novi robusniji QSAR modeli razvijeni su na nekoliko tisuća kemikalija iz baza ToxCast i Tox21 s brojnim i osjetljivijim toksičnim učincima izmjerenim na staničnim linijama i embrijima zebrice. Novi modeli temeljeni su na molekularnim deskriptorima i strukturnim otiscima, a dobiveni su logističkom regresijom, neuronskim mrežama i slučajnim šumama koje su dale ponajbolje modele. Dobiveni modeli pokazuju dobru generalizaciju na vanjskim skupovima onečišćivala, a njihova kvaliteta provjerena je novouvedenim metrikama. Procjene ekotoksikološkog rizika od spojeva utvrđenih u rijeci Savi temeljena na novim modelima toksičnosti pokazuju dobro slaganje s postojećim metodama, uz značajno povećanje kemijskog strukturnog prostora kojeg pokrivaju.

Strobilurins, a commonly used class of fungicides, are known to impact an embryonic development of aquatic organisms and show toxicity to different soil organisms. Standard tests for soil invertebrates are usually limited to the assessment of endpoints like survival and number of juveniles, while hatching and embryotoxicity tests have emerged recently. Besides earthworms, enchytraeids are the most commonly used bioindicators of soil contamination. Their size and short life cycle makes them suitable for this type of research. The main aim of the study was to assess the impact of strobilurins on reproduction and hatching delay of enchytraeid Enchytreus crypticus. Standardised OECD reproduction tests with azoxystrobin (AS), pyraclostrobin (PS) and trifloxystrobin (TS) were conducted. A decreased number of juveniles and an increased number of unhatched cocoons in strobilurin treatments were recorded. TS was the most toxic in terms of reproduction (EC50 0.04 mg a.i./kg soil), followed by PS (EC50 1.85 mg a.i./kg soil) and AZ (EC50 93.10 mg a.i./kg soil). The use of synchronised cocoons enabled monitoring of hatching dynamics. After a standard 11-day exposure more than 90 % of cocoons were hatched in the control while in treated soil those values were lower. However, as hatching was monitored after that period (up to the 19th day) the percentage of hatched cocoons significantly increased with the time of exposure. Consequently, EC50 values changed. These results show that supplementary endpoints such as hatching success included in standard tests could increase tests sensitivity and accuracy

Strobilurin fungicides (SFs) are a group of new fungicides produced by strobilurin A as a lead compound. Azoxystrobin, best-selling SF, is a highly efficient broad-spectrum fungicide with relatively high-water solubility, which may lead to accumulation in water, sediments, and soil. Due to its wide application and impact on non-target soil organisms azoxystrobin have attracted attention. Soil dwelling organisms are among the first in line of exposure to pesticides, however their risks are often based on the pure active ingredient (AI) and not on the commercial products (CPs) actually applied in the field. Enchytraeus albidus is a model species in soil ecotoxicology used for environmental risk assessment. Due to their important role in proper soil functioning, it is essential to investigate the toxicity and adverse effects of fungicides used in agriculture on enchytraeids. Previous research has demonstrated a negative impact of azoxystrobin on the reproduction and oxidative status of earthworms, and survival, reproduction, and hatching success in enchytraeids. However, most studies have assessed the effect of AI, while only a few used a CP. Therefore, we investigated the effects of pure AI, azoxystrobin, and CP Quadris on the survival, reproduction, oxidative stress biomarkers, energy metabolism, and MXR activity in E. albidus. Results showed that CP exhibited higher toxicity in terms of survival (LC50= 16.7 mg CP/kg soil, LC50= 15.3 mg AI/kg soil), while reproduction was affected only by CP (EC50= 3 mg CP/kg soil). Furthermore, although both tested substances caused oxidative stress, the toxicity of the CP was higher. Exposure to CP and AI affected energy metabolism, causing changes in lipid and carbohydrate content. Moreover, while AI caused induction of the multixenobiotic resistance system, CP caused inhibition. These results suggest the importance of evaluating the effect of AI and CP. Furthermore, to obtain more accurate information on the mode of action, access through different endpoints is required. These findings highlight the need to further explore the toxicity of CPs compared to AIs, aiming to predict a more ealistic environmental hazard of fungicides.

Arsen je polumetal (element 15. skupine elemenata u Periodičkoj tablici elemenata), te je očekivano da će tvoriti čitav niz spojeva različitih svojstava s obzirom na vrstu kemijske veze i strukturu. U kemijskim reakcijama iskazuje metalna i nemetalna svojstva. S obzirom na Paulingov koeficijent elektronegativnosti sličan nemetalima, tvori stabilne kovalentne spojeve i s najelektronegativnijim elementima, u spojevima stvara stabilnu kovalentnu vezu As–As te tvori organoarsenove spojeve sa stabilnom vezom As–C. Primjena arsenovih spojeva bila je u prošlosti raznovrsna i višestruka. Povijesni pregled otkrivanja i uporabe arsenovih spojeva jasno poučava da se razvoj spoznaja o kemiji arsena i arsenovih spojeva temelji na znanstvenim otkrićima i napretku znanosti općenito. Organoarsenovi spojevi u prošlosti rabljeni kao lijekovi, kasnije su, razvojem znanosti, odbačeni kao otrovni i zamijenjeni naprednijim, modernijim lijekovima čija se svojstva i uporaba više ne zasnivaju na empiriji. Anorganski spojevi arsena (posebice arsenovi sulfidni minerali) primjenjivali su se kao anorganski pigmenti u slikarstvu. Takvi primjeri upotrebe spojeva kroz povijest mogu se primijeniti u srednjoškolskoj nastavi kao primjer međupredmetnih tema u kojima se povezuje kemija arsena s ekološkim i toksikološkim temama te u povijesti umjetnosti. Slično postoji i u visokoškolskom obrazovanju, posebice gdje se izučava primijenjena anorganska kemija ili u povijesti medicine i farmakologije. Ovo djelo je dano na korištenje pod licencom Creative Commons Imenovanje 4.0 međunarodna., Arsenic is metalloid (element of the 15th group of elements in the Periodic table of elements), and it is expected to form a series of compounds with different features regarding the type of chemical bond and structure. As a metalloid, it exhibits metallic and non-metallic character in chemical reactions. Arsenic is able to form covalent compounds with elements of high electronegativity considering its Pauling’s electronegativity coefficient, which is comparable to those of the non-metals, and is able to form stable As–As and As–C covalent bonds in compounds. Applications of arsenic compounds in the past have been various and multiple. The historical review of discoveries and usages of arsenic compounds clearly shows that development of arsenic chemistry is founded on scientific discoveries and improvement of science in general. The medicines in the past, and later, by scientific progress, many arsenic compounds had been rejected as toxins and replaced with more progressive, modern medicines, the features and usage of which are not based on experience of doctors and pharmacists any longer. The inorganic compounds of arsenic (especially some arsenic sulphide minerals) had been used as inorganic pigments in the art of painting. Such examples of usage of compounds through history can be used in high school education as part of intercourse themes, thus joining the chemistry of arsenic with ecological and toxicological themes, as well as the history of art. The same goes for higher education, particularly within applied chemistry courses of arsenic or within the history of medicine and pharmacology. This work is licensed under a Creative Commons Attribution 4.0 International License.

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.

V pričujoči raziskavi smo proučevali vpliv dveh motilcev endokrinega sistema (MES): fenola bisfenol-A (BPA) in umetnega estrogena etinilestradiol (EE2), ki ju je moč, zaradi narave njune uporabe, pogosto najti v okolju. Njune učinke smo proučevali na vodnih bolhah vrste Daphnia magna, in sicer z uporabo dveh metod za ugotavljanje strupenosti: 1) test akutne strupenosti po ISO 6341:2012 in 2) test kronične strupenosti po OECD Guideline no. 211. Pri slednjih smo poleg učinkov BPA in EE2 posamično preverjali tudi učinke njunih mešanic. Za akutne teste z BPA smo izračunali 24 h EC50 in 48 h EC50. Ker pri testiranih koncentracijah EE2 ni bilo učinkov, zanj teh vrednosti nismo izračunali. Pri kroničnih testih smo poleg števila gibljivih juvenilnih osebkov na samico opazovali še vpliv na pogostost levitev in velikost samic ob koncu testa. Ugotovili smo signifikantne učinke koncentracije BPA 10 mg/L na število juvenilnih osebkov na samico in na končno velikosti le-teh, tako pri testih s posamičnimi snovmi kot tudi v mešanicah. Signifikanten učinek na levitev samic se je pokazal le pri testu z mešanico 10 mg/L BPA in 1 μg/L EE2. Ob nižji koncentraciji BPA (1 mg/L) učinki niso bili signifikantni, kot tudi ne pri testih z EE2 posamično. Ugotovili smo, da MES spreminjajo reprodukcijski potencial in zmanjšujejo reprodukcijsko sposobnost teh testnih vodnih organizmov. The aim of this study was to look into the effects of the phenol bisphenol A (BPA) and the artificial estrogen ethinyl-estradiol (EE2), two endocrine disrupting compounds (EDCs), which are obiquitous in the environment, as a consequence of their usage. We examined their effects on the water flea Daphnia magna, using two methods for toxicity-testing: 1) an acute toxicity test as per ISO 6341:2012 and 2) a chronic toxicity test as per OECD Guideline no. 211. For the later we also tested the effects of mixtures of these compounds. We calculated the 24 h EC50 and 48 h EC50 values for the acute toxicity tests for BPA, which was not possible for EE2, because of a lack of quantifiable effects. In our chronic tests, we looked into the effects of our test-compounds on the number of mobile juveniles per female, the molting-frequency of the later and their size at the end of the tests. We found significant effects of tests with BPA at 10 mg/L (individualy and in mixtures) on the number of mobile juveniles per female and on the end-of-test size of the females, but not on their molting-frequency, with the exception of a mixture with 10 mg/L BPA and 1 μg/L EE2. Tests with a BPA concentration of 1 mg/L individualy and in mixtures did not show any significant effects, which also holds true for tests with EE2 individualy. We concluded that EDCs impact the reproductive potential and lower the reproduction-abilty of the aquatic organisms used in this study.

Farmaceitiskās vielas ir ķīmiski savienojumi, kas ir plaši izmantoti cilvēku un veterinārajā medicīnā. Pieaugot farmaceitisko līdzekļu ražošanai un izmantošanai, arī palielinās aktīvo farmaceitisko vielu (FAV) klātbūtne ūdens ekosistēmās, radot potenciālu apdraudējumu videi. Darba mērķis ir noteikt Latvijas virszemes un notekūdeņos izplatītāko farmaceitiski aktīvo vielu koncentrāciju individuālo ekotoksikoloģisko ietekmi uz vienšūnu zaļaļģēm Desmodesmus subspicatus Notekūdeņu un virszemes ūdeņu paraugiem, kas ievākti Lielupes sateces baseinā tika noteiktas FAV koncentrācijas. Pēc datu analīzes tika izvēlētas sešas FAV ar paaugstinātu koncentrāciju no trim terapeitisko līdzekļu grupām – antibiotikas, pret iekaisuma līdzekļi un CNS ietekmējošie līdzekļi, lai noteiktu to individuālo ekotoksikoloģisko ietekmi uz vienšūnu zaļaļģu Desmodesmus subspicatus augšanas inhibīciju. Iegūtie rezultāti parāda, ka virszemes ūdeņu un notekūdeņu FAV koncentrācijas uzlaboja (ketoprofēns, levetiracetāms, gabapentīns) vai neietekmēja (diklofenaks, trimetoprīms, klaritromicīns) Desmodesmus subspicatus augšanu. Neskatoties uz to, augošā FAV klātbūtne vidē ir jāņem vērā un ir nepieciešami turpmāki pētījumi, lai iegūtu labāku izpratni un zināšanas par to ietekmi uz vidi., Pharmaceuticals are chemical compounds that are widely used in human and veterinary medicine. Due to increasing production and use of pharmaceuticals, also increases presence of active pharmaceutical ingredients (APIs) in aquatic ecosystems, creating potential threat to environment. Aim of this study is to detect effect of individual APIs surface water and waste water concentrations on Desmodesmus subspicatus growth inhibition. Wastewater effluent and surface water samples were collected in Lielupe River catchment area and API concentration were detected. After data analysis six APIs with increased concentrations from three therapeutic groups – antibiotics, anti-inflammatory agents and antiepileptics, were selected for individual API effect determination on Desmodesmus subspicatus growth inhibition. Results showed that surface water and wastewater API concentration improved (ketoprofen, levetiracetam, gabapentin) or did not affect (diclofenac, trimethoprim, clarithromycin) growth of Desmodesmus subspicatus. Nevertheless, the increasing presence of API in the environment must be taken in consideration and further studies are needed to obtain better understanding and knowledge of environmental impact of APIs.

Helsinku Komisija 2017. gadā publicējusi pārskatu par farmaceitiski aktīvo vielu (FAV) sastopamību, veidiem un piesārņojuma cēloņiem ūdeņu sistēmās periodā no 2003.gada līdz 2014. gadam. Dati par Latviju tajā nebija iekļauti. Darba mērķis ir izvērtēt sirds un asinsavadu (kardiovaskulāro) farmaceitiski aktīvo vielu vides ietekmes riskus virszemes ūdeņos un notekūdeņos Latvijā. Mērķa sasniegšanai apkopota kardiovaskulāro FAV ekotoksikoloģisko informāciju un izvērtēt vides piesārņojuma riski astoņām kardiovaskulāro FAV grupām. Rezultāti liecināja, ka Latvijā augsts vides risks atorvastatīnam (seruma lipīdus modificējošie līdzekļu grupa) savukārt vidējs risks ir gemfibrozilam (fibrātu grupa). Citām darbā apskatītajām vielām vides risks ir zems. Nepieciešami papildus pētījumi, lai precīzāk precīzāk izvērtētu FAV iespējamos vides riskus., Helsinki Commission in 2017 has published status report on active pharmaceutical ingredient (API) occurrence, types and pollution causes in the Baltic Sea region during period 2003 - 2014. Data of Latvian region had not been included. The aim of this study is to evaluate environmental risks of heart and cardiovascular disease treatment APIs in surface and waste waters in Latvia. To analyse ecotoxicological effects and environmental pollution risk, available information on eight API groups for cardiovascular disease treatment was gathered. Results show that in Latvia atorvastatin (serum lipid-modifying medication group) has high environmental risk and gemfibrozil (fibrate group) has medium risk. Environmental risk of other detected APIs is low. Further research need to be done in order to assess more detailed potential environmental risks of the APIs.

Zbog svoje primjene u akvakulturi, alge dobivaju sve više pozornosti kao održiv izvor korisnih produkata. Budući da mikroalge imaju važnu ulogu kao primarni proizvođači u vodenim ekosustavima i osnova su mnogih prehrambenih lanaca, važno je razumjeti procese koji im omogućuju bolje preživljavanje u toksičnom okolišu. Cilj ovog rada je evaluirati metodu Chlorella testa: (1) kao potencijalnu metodu za uzgoj algi, (2) kao metodu za procjenu prednosti i nedostataka života u simbiotskoj asocijaciji, uključujući dvije vrste aposimbiotskih algi (endosimbiotske alge prethodno izolirane iz zelene hidre) (Mychonastes homosphaera (Skuja) Kalina i Punčochářová i Desmodesmus subspicatus (Chodat) Hegewald i Schmidt te dvije vrste algi kao njihovih slobodnoživućih srodnika Chlorella kessleri Fott i Novak. [K&H, 1992] i C. vulgaris Beij. [K&H, 1992]), (3) s obzirom na odgovore algalnih bioindikatora povezane s komparativnom toksičnošću i ekotoksikološkim onečišćenjem željezom, i (4) putem korištenja algalnih bioindikatora za mikroskopijsku i morfometrijsku primjenu u okolišnom stresu. Povišenjem koncentracije željeza pojavile su promjene na stanicama (nakupine suhih umirućih stanica, mukozne strukture intenzivno zelenih mjehurića vlage, površina, promjer i duljina), deformacije (prazne stanice, nepotpune diobe, nepravilni cenobiji, tetrade i prijelazni oblici) i ultrastrukturne promjene (kloroplasti i jezgre). Sve promjene su bile izraženije u aposimbiotskih algi, što ukazuje na niži stupanj prilagođenosti na toksičnost željeza od njihovih slobodnoživućih srodnika. Slobodnoživuća vrsta C. kessleri se pokazala najprilagođenijom vrstom. Uočena je visoka statistička značajnost razlike u parametru stanične diobe, što ističe hormestički učinak povećanja biomase u slobodnoživućih vrsta algi. Ovo povećanje biomase pri specifičnoj koncentraciji željeza ukazuje na činjenicu da se Chlorella test može uspješno koristiti za vrednovanje rasta različitih mikroalgalnih vrsta i pokazuje perspektivnu primjenu u komparativnim studijama uzgoja različitih vrsta algi., Algae are gaining attention for their application in aquaculture as a highly sustainable source of useful products. As microalgae have a significant role in primary production in aquatic ecosystems and are the basis of many food chains, it is important to understand the processes that provide them with better survival in a toxicant-polluted environment. In this study the Chlorella bioassay was evaluated: (1) as a potential method for algae farming, (2) as a method for testing advantages or disadvantages of symbiotic association, including two species of aposymbiotic algae, i.e. endosymbiotic algae isolated from green hydra Mychonastes homosphaera (Skuja) Kalina and Punčochářová and Desmodesmus subspicatus (Chodat) Hegewald and Schmidt) and two related free-living algal species (Chlorella kessleri Fott and Novak. [K&H, 1992] and C. vulgaris Beij. [K&H, 1992]), (3) through algal bioindicator responses related to comparative toxicity and ecotoxicological pollution of iron, and (4) by using algal bioindicators for microscopical and morphometrical application in environmental stress. Increasing concentrations of iron led to cell changes (dry dotted clusters of dying cells, intensive green wet bubbles representing a mucous structure, area, diameter and length), deformations (empty cells, aberrant divisions, irregular coenobia, tetrads and transitional forms) and ultrastructural changes (chloroplasts and nuclei). All modifications were more pronounced in aposymbiotic algae, suggesting a lower degree of adaptation to iron toxicity than their free-living relatives. A free-living species C. kessleri showed the best ability to survive in given unfavorable environmental conditions. High statistical significance was noticed in the cell division parameter, underlining the hormetic effect of increasing the biomass in free-living algal species. This increasing of the cell divisions at the specific concentration of iron demonstrated that the Chlorella bioassay may represent a useful tool for evaluating the growth of different microalgal species, and has a prospective application in a comparative study of algae farming.

Obale, mora i oceani mjesta su intenzivnih ljudskih aktivnosti koje predstavljaju izvor kemijskog i biološkog onečišćenja. Kao posljedica javlja se degradacija obalnih i otvorenih zona te povećanje rizika za život u moru. Očekuje se da će u budućnosti obalna područja biti još ugroženija. S obzirom na dalekosežne posljedice učinaka potencijalno štetnih tvari na život u moru i oko njega, nužno je aktivno uključiti ljude u procese upravljanja morskim ekosustavom. Kako bi se moglo upravljati na učinkovit i ekološki prihvatljiv način, potrebne su ekotoksikološke procjene rizika prisutnosti onečišćivala. Za ostvarenje tih procjena nužno je iskustvo i znanje koje je najbolje početi usvajati tijekom studijske naobrazbe. Ovaj rad uključuje saznanja iz različitih znanstvenih disciplina, kao što su biologija mora, kemija mora, biokemija, toksikologija, ekologija, molekularna biologija, stanična biologija te evolucija. Također sadrži primjere i rezultate primijenjenih ekotoksikoloških istraživanja mora. Sadržaj je uobličen u tri cjeline izložene u jedanaest poglavlja. U prvoj cjelini čitatelj se upoznaje s potrebama, pristupima i načinima ekotoksikoloških istraživanja mora i oceana, pojmovima „onečišćivalo“ i „zagađivalo“ te njihovom sudbinom u morskom okolišu. U drugoj cjelini doznaje se kako različita onečišćivala i zagađivala utječu na život u morima i oceanima te kako stres djeluje na moguće evolucijske promjene. U trećoj cjelini čitatelj se upoznaje sa statističkom obradom rezultata ekotoksikoloških istraživanja mora, primjerima ekotoksikoloških istraživanja mora te načinima integriranog praćenja kvalitete morskog okoliša. Knjiga bi trebala biti referentna za studente koji ulaze u područje ekotoksikologije mora i oceana te u područja drugih znanosti o okolišu. Dijelovi knjige mogu služiti kao primjeren tekst za potrebe budućih znanstvenika te svih uključenih u upravljanje morskim okolišem i procjenom rizika, kao što su različita javna, upravna i politička tijela. Nadamo se da će ovo područje istraživanja svima zainteresiranima biti bliže i razumljivije nakon čitanja ove knjige.

Natrijev klorat(I), najdemo pod komercialnim imenom varikina. Najprej so ga uporabljali, kot belilno sredstvo, kasneje pa so ugotovili, da ima tudi protimikrobne učinke in ga zato še danes veliko uporabljajo v medicinske namene. Med prvo in drugo svetovno vojno so ga uporabljali tudi za razkuževanje ran in opeklin. Koncentracije, ki se uporabljajo v zdravstvu so zelo nizke in ne vplivajo škodljivo na ljudi in živali. Ker pa je kemikalija na trgu zlahka in po zelo nizki ceni dostopna, se lahko hitro zgodi, da se zaradi premalega ozaveščanja ljudi v okolje spustijo višje koncentracije, ki pa so strupene za vodne organizme. V okviru te diplomske naloge smo izvedli akutni test strupenosti na vodne bolhe (Daphnia magna), ki je bil povzet po smernici OECD. Imobilizacijo bolh smo opazovali po 24 in 48 urah in določili vrednost LC50. Daphnia magna je le ena od vrst, ki jih uporabljamo za standarnizirane teste in je bila za test izbrana na podlagi svojih morfoloških in fizioloških značilnosti. Za test je bila uporabljena 13 % vodna raztopina natrijevega klorata(I). Po pregledu literature smo našli kar nekaj podatkov o strupenosti natrijevega klorata(I) za živali. Viri navajajo, da je strupenost natrijevega klorata(I) odvisna predvsem od koncentracije in poti skozi katero vztopa kemikalija v telo. Sodium hypochlorite is found under the commercial name of bleach. It was first used as a bleaching agent, and it was discovered later on that it also has antimicrobial effects, which is why it is still widely used today for medical purposes. During the First and Second World Wars, it was also used for disinfecting wounds and burns. The concentrations used in healthcare are very low and do not have a harmful effect on humans and animals. However, since the chemical is easily accessible on the market at a very low price, it can quickly occur that due to the lack of awareness in people, higher concentrations, which are potentially toxic to aquatic organisms, are released in the environment. In the scope of this thesis, an acute toxicity test on water fleas (Daphnia magna) was conducted in accordance with the OECD Guideline. The immobilisation of the animals was observed after 24 and 48 hours and the LC50 value was determined. Daphnia magna is only one of the species used for standardized tests and it was selected due to its morphological and physiological characteristics. A 13 % aqueous solution of sodium hypochlorite was used for the test. Several literature sources report on the toxicity of sodium hypochlorite to animals. The data indicate that the toxicity of sodium hypochlorite depends primarily on the concentration and the pathway through which the chemical enters the body.

Rezime: Rezultati prezentovani u ovom radu predstavljaju doprinos poznavanju biodiverziteta lumbricida centralne Srbije. Takođe rezultati su dali uvid u, prvi put kod nas rađena, ekotoksikološka ispitivanja na ovim organizmima. Obavljena su kompleksna faunistička istraživanja lumbricidne faune na području centralne Srbije i objedinjeni su svi dostupni literaturni i terenski podaci. Terenskim radom na ovoj studiji, na istraživanim lokalitetima, u 160 sakupljenih uzoraka (2190 jedinki), registrovano je 16 taksona. Tokom ranijih istraživanja utvrđeno je prisustvo 44 taksona. Našim istraživanjima utvrđeno je prisustvo tri taksona koji ranije nisu bila konstatovana na prostorima centralne Srbije, tako da danas fauna lumbricida ovog prostora broji 47 taksona. Od ukupnog broja vrsta koje su konstatovane na teritoriji Srbije, skoro 60% vrsta je pronađeno u centralnoj Srbiji. Po prvi put u centralnoj Srbiji su registrovane tri vrste: Allolobophora parva, Aporrectodea cemernicensis (po drugi put registrovana na teritoriji Republike Srbije) i Lumbricus castaneus. Iako peregrina vrsta, A. parva je registrovana prvi put u Srbiji, što je od izuzetnog faunističkog značaja. Po prvi put, u našim istraživanjima Allolobophora serbica je pronađena u novom biotopu, šumskom, i to i u prolećnoj i u jesenjoj sezoni. Da bi se zoogeografski što jasnije shvatila struktura lumbricidne faune centralnog dela Srbije, neophodno je bilo izvršiti kategorizaciju. Naša analiza je pokazala da najveći broj vrsta pripada peregrinim vrstama (38,30%). Endemičnih vrsta ima 19,15%. Zatim slede trans-egejske vrste (12,77%), centralno-evropske (10,64%), alpsko-balkanske (10,64%), i nešto manje približno mediteranske (4,26%) i atlansko- mediteranske (2,13%). Istraživanja koja su sprovedena u okviru ekotoksikološkog dela zasnovana su na hipotezi da pesticidi u životnoj sredini pored ciljanih organizama utiču i na neciljane organizme, što se kroz lance ishrane odražava i na više trofičke nivoe, a u krajnjem ishodu i na čoveka. Laboratorijski testovi su sprovedeni na osnovu smernica OECD-a. U ovim testovima toksičnosti koristili smo vrstu Eisenia fetida, kao test organizam, koju smo izlagali, u veštačkom test zemljištu, različitim koncentracijama ispitivanih pesticida, zasnovanim na preporučenim poljoprivrednim dozama. Testirani su pesticidi koji su lokalno najviše u upotrebi, među kojima je i bioracionalni insekticid Laser (spinosad) koji se po prvi put ispitivao na vrsti E. fetida. Svaki od pesticida pokazao je drugačiji stepen toksičnosti, a jedino je u kontrolnim tretmanima bilo 100% preživelih kišnih glista evidentiranih do kraja eksperimenata. Piretroidi su poznati po domino efektu i izrazitoj početnoj efikasnosti. U našim eksperimentima smo već u prvoj nedelji zabeleželi smrtnost glista u svim koncentracijama. Ipak, izračunate LC50 vrednosti su bile više od najviše koncentracije. Od svih korišćenih piretroida (Cipkord, Talstar, Laser), Laser se pokazao kao ekološki najbezbedniji. Rezultati toksikoloških istraživanja pokazuju da su gliste na osnovu krajnjih tačaka kao što su rast i reprodukcija veoma osetljive na ispitivane herbicide (Terbis, Kalisto, Ekvip, Adengo). Bez obzira, što ne utiču na mortalitet, utiču na subletalne krajnje tačke, koje su znatno osetljiviji parametri za procenu, što u dužem vremenskom intervalu, znači uticaj na samu populaciju glista. Summary: The results presented in this paper is contribution to the knowledge of biodiversity Lumbricidae central Serbia. Also, the results were gave an insight into ecotoxicological testing on earthworm which is the first of that kind investigations in our country. The complex faunistic research of earthworm fauna in the area of central Serbia was performed and all available literature data and field data are summarized. Based on field work in the investigated area have been registered 16 taxa in 160 samples (2190 individuals). In previous studies revealed the presence of 44 taxa. Our research has revealed the presence of three taxa that have never been ascertained on the territory of central Serbia. Therefore, today Lumbricidae fauna of this area consists of 47 taxa. Of the total number of earthworm species that are found in the territory of Serbia, almost 60% of the species is found in the area of central Serbia. Three species are registered for the first time in central Serbia: Allolobophora parva, Aporrectodea cemernicensis (registered on the territory of the Republic of Serbia only in eastern and central Serbia) and Lumbricus castaneus. Also, it is interesting that peregrina species A. parva is registered for the first time in Serbia, which is of great faunal significance. For the first time, in our research, Allolobophora serbica is found in a new biotope, forest, both in the spring and the autumn seasons. In order to better understand the zoogeographical structure of Lumbricidae from the central part of Serbia, categorization was required. Our analysis showed that most of them are Peregrine species (38,30%). The percent of endemic species is 19,15%, followed by Trans - Aegean (13,77%), Central-European (10,64%), Balkanic-Alpine (10,64%), and a little less Circum-Mediterranean (4,26%) and Atlantic-Mediterranean (2,13%). Researches conducted in the framework of ecotoxicology part are based on the hypothesis that pesticides in the environment have impact, not only to the target organisms, but also to the non-target organisms, which through food chains may produce damages to higher trophic levels, and ultimately to the man. The laboratory test was conducted according to the OECD guidelines. To assess the toxic effects of pesticides on non-target organism, we exposed the earthworm Eisenia fetida to artificial soil supplemented with different concentrations of the examined pesticides based on the recommended agricultural doses. The tested pesticides that are mostly used locally, including the insecticide Laser (spinosad). This is the first report about effects of spinosad on the life-cycle parameters on non-target organism, earthworm E. fetida. Each of used pesticide showed a different degree of toxicity. Only in the control treatment was 100% survival of the earthworms recorded until the end of experiments. Pyrethroids are known by knock-down effect and expressed initial efficacy. In the first weeks, we have immediately recorded mortality of earthworms in all concentrations. However, the LC50 values were higher than the highest concentrations which we used in the experiment. Of all the used pyrethroids (Cipkord, Talstar, Laser), Laser has proven to be as environmentally safest. Based on the endpoints such as growth and reproduction, the results of toxicological research show that the earthworms are very sensitive to the tested herbicide (Terbis, Callisto, Ekvip, Adengo). Regardless, it does not affect mortality, affecting sublethal endpoints, which are much more sensitive parameters for assessing, which a longer time interval means the impact on itself population of earthworms.

Vodeni ekosustavi su pod stalnim pritiskom antropogenih onečišćujućih tvari koje potječu iz različitih izvora. Utjecaj toksikanata vidljiv je na molekularnoj i staničnoj razini biološke organizacije, ali i na razini čitavog organizma, populacije i zajednice. Za praćenje učinaka uzrokovanih ljudskim djelovanjem na zdravstveno stanje vodenog okoliša koristimo biomonitoring. On uključuje upotrebu biomarkera i bioindikatorskih vrsta koji zadovoljavaju određene kriterije, a čije nam proučavanje može dati informacije o promjenama određenih toksikanata u okolišu tijekom vremena. Životinjski, mikrobni i kontaminanti iz okoliša glavne su vrste toksikanata u moru. Mekušci su, posebice školjkaši, najčešće upotrebljavani kao biološki indikatori zagađenja. Oni zauzimaju važnu poziciju u hranidbenom lancu, široko su geografski rasprostranjeni, relativno dugog životnog vijeka, odgovarajućih dimenzija, veličine, težine, jednostavno se identificiraju, prikupljaju i lako održavaju u laboratorijskim uvjetima. Sjedilački su organizmi koji akumuliraju u svoje tkivo mnoge ksenobiotike: pesticide, ugljikovodike, metale i druge tvari prisutne u vodi koja ih okružuje. Tjelesno opterećenje metala u mekušcima i trajna kontrola kvalitete vode dobri su pokazatelji kvalitete okoliša te se mogu se upotrijebiti za predviđanje toksičnog utjecaja poznatih ili nepoznatih ksenobiotika.

The reaction between hypochlorous acid (HOCl) and 5-fluorouracil (5-FU) is the fundamental process which can occur in activated neutrophils in cancer patients or during chemical treatment of (hospital) wastewaters . Therefore, the chlorination of 5-FU is of utmost importance in medicinal and environmental chemistry. In this work, it is experimentaly shown that the first product of 5-FU chlorination process is chlorohydrine, which undergoes further chlorination. Structural characteristics of products are determined using 1H, 19F and 13C NMR spectroscopy. Reaction mechanism of chlorination cascade of 5-FU is investigated using quantum chemistry methods. M06–2X/6– 311++G(3df, 2pd)//M06–2X/6–311+G(d) level of theory is applied. The solvent effects are described by the implicit SMD solvation model, using the optimal number of the explicit water molecules. It is shown that 5-FU is chlorinated at the C5 position in the pyrimidine ring. The two-steps reaction in which the first reaction is the addition of Cl+ on N1 anion of 5-FU, yielding the imine intermediate, is determined as the most feasible mechanism. The free energy barrier which corresponds to the addition of chloronium ion is 72, 9 kJ/mol. The addition of water on the imine intermediate (deltaG‡ = 21, 0 kJ/mol), which results in the chlorohydrine, is the second reaction step. The results obtained with quantum chemical methods are in agreement with experimental data. Standard bioassays are preformed in order to determine ecotoxicity of chlorination products of 5-FU. Results of these study play a key role in predicting the environmental fate of 5-FU.

Eutektična otapala su smjese akceptora i donora vodikove veze, a imaju temperaturu tališta mnogo nižu od temperature tališta pojedinačnih komponenata smjese. Zbog svojih jedinstvenih fizikalno-kemijskih svojstava, niske cijene i široke mogućnosti primjene eutektična otapala su u fokusu interesa posljednjih godina. Industrijska upotreba eutektičnih otapala može se očekivati u bližoj budućnosti obzirom na veliku mogućnost primjene u području zelenih tehnologija, no prije upotrebe u velikom mjerilu, njihov utjecaj na okoliš te biorazgradivost i toksičnost mora se detaljnije istražiti.U ovom radu ispitan je utjecaj osam eutektičnih otapala na preživljenje humane stanične linije MCF-7 primjenom kolorimetrijske MTS metode. Na temelju dobivenih rezultata možemo zaključiti da ispitana eutektična otapala nemaju inhibitoran učinak na rast MCF-7 stanica te posjeduju nisku citotoksičnost. Deep eutectic solvents are mixtures of hydrogen bond aceptors and hydrogen bond donors with a melting point much lower than that of either of its components. They have been in the focus of interest in the last years due to their unique properties, low cost and wide range od applications. Their industrial usage can be expected in the future based on numerous potencial DESs applications in the green technologies, therefore environmental impact and fate of DESs has to be investigated in more details. In this final work the impact of eight DESs on human cell line MCF-7 was tested by MTS method. Based on the results, we can conclude that these DESs have no inhibitory effect on MCF-7 cells and therefore possess low cytotoxicity.

Crni američki patuljasti som (Ameiurus melas Rafinesque, 1820) je najzastupljenija i najuspešnija alohtona vrsta ribe koja naseljava kopnene vode Evrope. Istraživanja koja su sprovedena u proteklih nekoliko godina ukazuju na to da je ovo dominantna invazivna vrsta i u mnogim kopnenim vodama u Srbiji. Cilj istraživanja se odnosio na ispitivanje populacionih atributa patuljastog soma u Savskom jezeru, kao i na bioakumulaciju teških metala i mikroelemenata u različitim tkivima. Terenska istraživanja vršena su u periodu od 2009. do 2012. godine. Jedinke su uzorkovane jednom mesečno, četiri dana za redom. Laboratorijska obrada prikupljenih uzoraka obuhvatila je merenje totalne dužine tela (TL) i ukupne težine tela ulovljenih primeraka. Nakon disekcije jedinki merena je težina tela bez utrobe, kao i masa jetre i gonada.Struktura populacije utvrđena je kombinovanjem dve metode – analizom starosti jedinki i analizom dužinskih frekvencija. Starost jedinki određena je takođe uz pomoć dve metode – očitavanjem naraštajnih zona otolita i Batačarija metodom. Analiza uzrasne strukture populacije pokazala je prisustvo pet uzrasnih kategorija: od 0+ do 4+. Klasa 1+ bila je najdominatnija uzrasna klasa, kako po godinama, tako i po sezonama uzorkovanja. Prosečna totalna dužina jedinki iznosila je 13,3 cm, a prosečna težina 38,26 g. Prosečna relativna težina jedinki u Savskom jezeru, u celokupnom uzorku, iznosila je 84,78 ± 1,09 g. Utvrđeno je prisustvo ukupno 8 kohorti. Na osnovu analize dužinsko-težinskih odnosa izračunate su i vrednosti faktora alometrije b koje su se kretale od 2,93 do 3,16, dok je vrednost ovog faktora u celom poduzorku iznosila 3,00. Analizom krive dužinsko-težinskog odnosa utvrđeno je da tačka infleksije ne postoji. Ribolovni napor (CPUE) je korišćen za analizu distribucije i relativne gustine jedinki, kako po staništima, tako i po godinama uzorkovanja i sezonama. Tokom 2009, 2010. i 2012. godine CPUE vrednosti varirale su od 0,4 ± 0,5 do 41,5 ± 22,1 jedinki po vrši po danu... abundant and successful non-native fish species in European freshwaters. Recent studies indicate that the black bullhead is one of the most dominant invasive fish species in Serbian waters as well. The aim of this research was to determine the population characteristics of this species in Sava Lake, as well as bioaccumulation of heavy metals and trace elements in different tissues. Fieldwork was conducted from 2009 to 2012. Black bullhead samples were collected monthly, for four days in a row. Once in the laboratory, specimens were measured for their total length (TL) and body weight (W). After dissection, the eviscerated body weight was measured, as well as liver and gonad weights. Population structure was determined by combining two methods – analyzing age and length-frequency distributions. Age was determined by combining otolith examination and Bhattacharya’s method. Age structure analysis has revealed the presence of five age classes: from 0+ to 4+. The class 1+ was the most dominant, by both year and season of sampling. The average total length was 13.3 cm and the average weight was 38.26 g. The mean value of the relative weight, across the entire sample, was 84.78 ± 1.09. The research revealed the presence of eight cohorts, in total. The length-weight allometric factor b ranged from 2.93 to 3.16, while the value of this factor, across the entire sample, was 3.00.The analysis of the length-weight relationship curve showed an absence of inflection points. Catch-per-unit-effort (CPUE) was used as an indicator of the black bullhead distribution and abundance in different habitats, years of sampling, and seasons. In 2009, 2010, and 2012, CPUE values fluctuated and ranged from 0.4 ± 0.5 to 41.5 ± 22.1 ind./net/night, while in 2011 they were low and rather uniform, ranging from 0.2 ± 0.3 to 3.4 ± 4.5 ind./net/night. CPUE values were highest in the macrophyte vegetation zone, as well as during autumn and spring...

U okviru ove disertacije ispitana je degradacija 4CP (para-hlorfenol), reaktivnih azo boja i ibuprofena primenom unapređenih oksidacionih procesa (eng. Advanced Oxidation Processes, AOP) kao što su Fentonov reagens, DBD reaktor (eng. Dielectric Barrier Discharge) i elektrohemijske degradacije. Efikasnost degradacija zagađujućih organskih supstanci optimizovana je dodatkom homogenog katalizatora (Fe2+ ili H2O2) u reaktor, primenom različitih elektrodnih materijala ili variranjem vremena tretmana. Dekolorizacija (%) je praćena UV-VIS tehnikom, efikasnost degradacije je praćena jonskom hromatografijom (IC) i HPLC tehnikom. Identifikacija glavnih proizvoda degradacije, kao i mehanizmi degradacije određeni su LC-MS (TOF) tehnikom. Efikasnost mineralizacije je određena preko TOC vrednosti. Tretman netermalnom plazmom (eng. non-thermal plasma NTP) u DBD reaktoru je ispitan tokom degradaciji 4CP do biodegradabilnijih i manje toksičnih intermedijera. Eksperimentalni rad je organizovan u tri sistema za degradaciju 4CP: DBD, DBD/H2O2 i DBD/Fe2+. Praćena je efikasnost degrdacije 4CP u funkciji broja prolaza kroz DBD reaktor, kao i količini unete energije po jedinici zapremine rastvora (gustina energije, kJ/L). Koncentracija 4CP, kao i koncentracija pojedinih proizvoda degradacije merena je nakon svakog prolaza. Koncentracije proizvoda degradacije 4CP kao što su sirćetna, mravlja ili oksalna kiselina, bile su niže u sistemu gde je kao katalizator upotrebljeno gvožđe DBD/Fe2+ u poređenju sa sistemom gde je kao katalizator primenjen vodonik-peroksid DBD/H2O2. Koncentracija hlorida u sva tri sistema je rasla tokom procesa degradacije. Najviša koncentracija hlorida, zabeležena je u sistemu sa dodatkom Fe2+ kao katalizatora. Procena toksičnosti početnog rastvora 4CP, kao i rastvora tretiranih u sva tri sistema ispitana je pomoću A.salina. U odnosu na početni (netretirani) rastvor 4CP, nakon tretmana DBD/Fe2+ porcenat preživelih larvi A. salina se povećao za 95%. Degradacija reaktivnih azo boja (RG15, RY125 i RB52) je ispitana primenom EAOP (eng. Eletrochemical Advance Oxidation Processes) tehnika u nepodeljenoj dvoelektrodnoj ćeliji, gde je kao anoda primenjena Fišerova platinska elektroda, a kao katoda korišćena je Pd, Zr ili C elektroda. Najefikasniji sistem za degradaciju RG15 i RY125 je bio Pt-Pd sistem, dok je za RB52 to bio Pt-Zr sistem. Ekotoksikološki efekat za boje RG15 i RY125 bio je najniži ili nije detektovan u rastvoru boje nakon Pt-Pd tretmana. U slučaju RB52, uočeno je da se ekotoksikološki efekat uvećava i na A.salina i na V.fischeri nakon EAOP tretmana. U slučaju degradacije ibuprofena, nakon 15 min tretmana dodatak homogenog katalizatora je poboljšao NTP tretman i doprineo efikasnosti degradacije ibuprofena (99%), kao i mineralizaciji zagađujuće supstance u odnosu na DBD i Fentonov proces (oko 80%). U svim tretmanima analizom masenih spektara, identifikovano je 12 proizvoda degradacije ibuprofena: pet aromatičnih i sedam alifatičnih proizvoda. Nakon DBD/Fe2+ tretmana detektovane su samo 4 alifatične karboksilne kiseline. Ekotoksikološki efekat tretiranih rastvora ibuprofena u DBD reaktoru nije detektovan, kao ni u slučaju kada je gvožđe korišćeno kao katalizator. U odnosu na A.salina, V.fischeri je pokazao veću osetljivost na proizvode degradacije koji su nastali tokom Fenton tretmana. Toksični efekat rastvora ibuprofena nakon Fenton tretmana kategorisan je kao klasa III, tj. “toksičan”. Najviši procenat degradacije ibuprofena primenom EAOP- a je postignut tretmanom rastvora u Pt - Pd sistemu - 98%, pri jačini struje od 100 mA i pH od 3. Toksični efekat mortalitet (%) A. salina izazvan rastvorom ibuprofena tretiranog u Pt-Pd sistemu bio je ispod 30% pri najvišoj testiranoj koncentraciji od 100% (c, v/v). V.fischeri se pokazao kao osetljiviji model za procenu toksičnog efekta proizvoda degradacije ibuprofena nakon Pt-Pd tretmana u odnosu na A.salina. In this thesis the degradation of 4CP (para-chlorophenol), reactive azo dyes and ibuprofen was studied using the Advanced Oxidation Processes (AOP) such as Fenton's reagent, Dielectric Barrier Discharge (DBD) reactor and electrochemical degradation. The efficiency of degradation was optimized by addition of a homogenous catalyst (Fe2+ or H2O2) to the reactor and also by applying different electrode materials or by varying the duration of the treatment. The decolorization (%) of reactive azo dyes was monitored by UV-VIS technique and the efficiency of degradation was monitored by ion chromatography (IC) and HPLC. Identification of the main degradation products as well as the degradation mechanisms were determined by LC-MS (TOF) technique. The mineralization efficiency was determined through the value of TOC. Treatment by non-thermal plasma (NTP) in the DBD reactor was studied during the degradation of 4CP to biodegradable and less toxic intermediates. Experimental work was organized into three systems for 4CP degradation: DBD, DBD/H2O2 and DBD/Fe2+ . The efficiency of 4CP degradation was evaluated by the number of passing of the solution through the DBD reactor, as well as the amountn of the introduced energy density (kJ/L). The concentration of 4CP, as well as the concentration of the individual degradation products were measured after the each pass. The concentrations of the 4CP degradation products such as acetic, formic or oxalic acid were lower in the system where the iron was used as the catalyst (DBD/Fe2+) in comparison to the system with hydrogen peroxide as the catalyst (DBD/H2O2). The concentration of chloride in all three systems increased during the degradation process. The highest concentration of chlorides was recorded in the system with the addition of Fe2+ as a catalyst. The toxicity assessment of initial solution of 4CP as well as the solution which has been treated in all three systems was performed using A.salina. In comparison to untreated solution of 4CP the solution treated in DBD/Fe2+ system had increased percentage of larval survival by 95%. Degradation of reactive azo dyes (RG15, RY125 or RB52) was studied using the EAOP (Eletrochemical Advance Oxidation Processes) techniques in undivided twoelectrode cell, where the Fisher platinum electrode was applied as anode and the Pd, Zr or C electrodes were applied as cathode. The most effective system for the degradation of RG15 and RY125 was Pt-Pd system, while for the RB52 the Pt-Zr system was more applicable. Ecotoxicological effect of reactive dyes RG15 and RY125 was the lowest or not detected in the dye solution after the Pt-Pd treatment. In the case of RB52 ecotoxicological effect increased for both A.salina and V.fischeri after the EAOP treatment. In the case of ibuprofen degradation, the NTP treatment (15 min) was improved by addition of a homogeneous catalyst, which contributed to the efficiency of degradation (99%) and the mineralization of polluting substances in comparison to DBD and the Fenton process (about 80%). After all treatments, by analysis of mass spectra 12 degradation products of ibuprofen were identified: five aromatic and seven aliphatic products. In the solution after the DBD/Fe2+ treatment only 4 aliphatic carboxylic acids were detected. Ecotoxicological effect of the ibuprofen solution treated in the DBD reactor as well as in the DBD/Fe2+ system was not detected. In relation to A.salina, V. fischeri has shown greater sensitivity to degradation products which appeared during the Fenton treatment. The toxic effect of ibuprofen solution after the Fenton treatment was categorized as class III, that is "Toxic". The highest degradation percentage of ibuprofen was achieved by application of EAOPs in the Pt - Pd system (98%), with the current of 100 mA and at the pH value of 3. The toxic effect expressed as the mortality (%) of A. saline was less than 30% at the highest tested concentration 100% (c, v/v) of ibuprofen solution treated in the Pt-Pd system. The V.fischeri was the more sensitive model for the assessment of the ibuprofen degradation products toxic effect after the Pt-Pd treatment in comparison to A.salina.

Kvalitativna istraživanja su primarna znanstvena istraživanja koja, nakon detekcije problema ili fenomena, kao rezultat donose hipoteze ili objašnjenja njihovih uzroka, mehanizama njihovog nastanka, te deskripcije njihovih posljedica. Kvantitativna istraživanja nalaze svoje hipoteze u rezultatima kvalitativnih istraživanja no njihov cilj je kvantifikacija problema ili fenomena u smislu generiranja podataka dostatnih za statističku analizu i, u najboljem slučaju, za matematički opis fenomena ili problema. Potreba postojanja kvalitetnih kvantitativnih podataka koji zadovoljavaju potrebe suvisle statističke analize vrlo često se u praksi smatraju formalnom potrebom pa se na taj način statističke metode i koriste. Zbog toga vrlo često među dobivenim rezultatima ostaju skriveni brojni implicitni podaci, fenomeni ostaju opisani na razini deskripcije, a problemi vrlo često bivaju rješavani na krivi način ili uz bespotrebnu štetu. U okviru ovog predavanja biti će najprije prikazana suština korištenja statističkih metoda i matematičkih modela kao korisnog i nužnog alata u ekotoksikološkim istraživanjima izvan okvira formalnih potreba. Nadalje, na nekoliko konkretnih primjera iz prakse, biti će prikazan razvoj ekotoksikoloških pokusa pomoću kvantitativnih metoda i premošćivanje jaza između tzv. teoretičara i eksperimentalista.

U okviru ove disertacije ispitana je degradacija 4CP (para-hlorfenol), reaktivnih azoboja i ibuprofena primenom unapređenih oksidacionih procesa (eng. Advanced OxidationProcesses, AOP) kao što su Fentonov reagens, DBD reaktor (eng. Dielectric BarrierDischarge) i elektrohemijske degradacije.Efikasnost degradacija zagađujućih organskih supstanci optimizovana je dodatkomhomogenog katalizatora (Fe2+ ili H2O2) u reaktor, primenom različitih elektrodnihmaterijala ili variranjem vremena tretmana. Dekolorizacija (%) je praćena UV-VIStehnikom, efikasnost degradacije je praćena jonskom hromatografijom (IC) i HPLCtehnikom. Identifikacija glavnih proizvoda degradacije, kao i mehanizmi degradacijeodređeni su LC-MS (TOF) tehnikom. Efikasnost mineralizacije je određena preko TOCvrednosti. Tretman netermalnom plazmom (eng. non-thermal plasma NTP) u DBDreaktoru je ispitan tokom degradaciji 4CP do biodegradabilnijih i manje toksičnihintermedijera. Eksperimentalni rad je organizovan u tri sistema za degradaciju 4CP: DBD,DBD/H2O2 i DBD/Fe2+. Praćena je efikasnost degrdacije 4CP u funkciji broja prolaza krozDBD reaktor, kao i količini unete energije po jedinici zapremine rastvora (gustina energije,kJ/L). Koncentracija 4CP, kao i koncentracija pojedinih proizvoda degradacije merena jenakon svakog prolaza.Koncentracije proizvoda degradacije 4CP kao što su sirćetna, mravlja ili oksalnakiselina, bile su niže u sistemu gde je kao katalizator upotrebljeno gvožđe DBD/Fe2+upoređenju sa sistemom gde je kao katalizator primenjen vodonik-peroksid DBD/H2O2.Koncentracija hlorida u sva tri sistema je rasla tokom procesa degradacije. Najvišakoncentracija hlorida, zabeležena je u sistemu sa dodatkom Fe2+ kao katalizatora.Procena toksičnosti početnog rastvora 4CP, kao i rastvora tretiranih u sva tri sistemaispitana je pomoću A.salina. U odnosu na početni (netretirani) rastvor 4CP, nakon tretmanaDBD/Fe2+porcenat preživelih larvi A. salina se povećao za 95%.Degradacija reaktivnih azo boja (RG15, RY125 i RB52) je ispitana primenomEAOP (eng. Eletrochemical Advance Oxidation Processes) tehnika u nepodeljenojdvoelektrodnoj ćeliji, gde je kao anoda primenjena Fišerova platinska elektroda, a kaokatoda korišćena je Pd, Zr ili C elektroda. Najefikasniji sistem za degradaciju RG15 iRY125 je bio Pt-Pd sistem, dok je za RB52 to bio Pt-Zr sistem. Ekotoksikološki efekat zaboje RG15 i RY125 bio je najniži ili nije detektovan u rastvoru boje nakon Pt-Pd tretmana.U slučaju RB52, uočeno je da se ekotoksikološki efekat uvećava i na A.salina i naV.fischeri nakon EAOP tretmana.U slučaju degradacije ibuprofena, nakon 15 min tretmana dodatak homogenogkatalizatora je poboljšao NTP tretman i doprineo efikasnosti degradacije ibuprofena (99%),kao i mineralizaciji zagađujuće supstance u odnosu na DBD i Fentonov proces (oko 80%).U svim tretmanima analizom masenih spektara, identifikovano je 12 proizvoda degradacijeibuprofena: pet aromatičnih i sedam alifatičnih proizvoda. Nakon DBD/Fe2+ tretmanadetektovane su samo 4 alifatične karboksilne kiseline. Ekotoksikološki efekat tretiranihrastvora ibuprofena u DBD reaktoru nije detektovan, kao ni u slučaju kada je gvožđekorišćeno kao katalizator. U odnosu na A.salina, V.fischeri je pokazao veću osetljivost naproizvode degradacije koji su nastali tokom Fenton tretmana. Toksični efekat rastvoraibuprofena nakon Fenton tretmana kategorisan je kao klasa III, tj. “toksičan”.Najviši procenat degradacije ibuprofena primenom EAOP- a je postignut tretmanomrastvora u Pt - Pd sistemu - 98%, pri jačini struje od 100 mA i pH od 3. Toksični efekatmortalitet (%) A. salina izazvan rastvorom ibuprofena tretiranog u Pt-Pd sistemu bio jeispod 30% pri najvišoj testiranoj koncentraciji od 100% (c, v/v). V.fischeri se pokazao kaoosetljiviji model za procenu toksičnog efekta proizvoda degradacije ibuprofena nakon Pt-Pdtretmana u odnosu na A.salina. In this thesis the degradation of 4CP (para-chlorophenol), reactive azo dyes andibuprofen was studied using the Advanced Oxidation Processes (AOP) such as Fenton'sreagent, Dielectric Barrier Discharge (DBD) reactor and electrochemical degradation.The efficiency of degradation was optimized by addition of a homogenous catalyst(Fe2+ or H2O2) to the reactor and also by applying different electrode materials or byvarying the duration of the treatment. The decolorization (%) of reactive azo dyes wasmonitored by UV-VIS technique and the efficiency of degradation was monitored by ionchromatography (IC) and HPLC. Identification of the main degradation products as well asthe degradation mechanisms were determined by LC-MS (TOF) technique. Themineralization efficiency was determined through the value of TOC.Treatment by non-thermal plasma (NTP) in the DBD reactor was studied during thedegradation of 4CP to biodegradable and less toxic intermediates. Experimental work wasorganized into three systems for 4CP degradation: DBD, DBD/H2O2 and DBD/Fe2+. Theefficiency of 4CP degradation was evaluated by the number of passing of the solutionthrough the DBD reactor, as well as the amountn of the introduced energy density (kJ/L).The concentration of 4CP, as well as the concentration of the individual degradationproducts were measured after the each pass.The concentrations of the 4CP degradation products such as acetic, formic or oxalicacid were lower in the system where the iron was used as the catalyst (DBD/Fe2+) incomparison to the system with hydrogen peroxide as the catalyst (DBD/H2O2). Theconcentration of chloride in all three systems increased during the degradation process. Thehighest concentration of chlorides was recorded in the system with the addition of Fe2+as acatalyst. The toxicity assessment of initial solution of 4CP as well as the solution which hasbeen treated in all three systems was performed using A.salina. In comparison to untreatedsolution of 4CP the solution treated in DBD/Fe2+ system had increased percentage of larvalsurvival by 95%.Degradation of reactive azo dyes (RG15, RY125 or RB52) was studied using theEAOP (Eletrochemical Advance Oxidation Processes) techniques in undividedtwoelectrode cell, where the Fisher platinum electrode was applied as anode and the Pd, Zror C electrodes were applied as cathode. The most effective system for the degradation ofRG15 and RY125 was Pt-Pd system, while for the RB52 the Pt-Zr system was moreapplicable. Ecotoxicological effect of reactive dyes RG15 and RY125 was the lowest or notdetected in the dye solution after the Pt-Pd treatment. In the case of RB52 ecotoxicologicaleffect increased for both A.salina and V.fischeri after the EAOP treatment.In the case of ibuprofen degradation, the NTP treatment (15 min) was improved byaddition of a homogeneous catalyst, which contributed to the efficiency of degradation(99%) and the mineralization of polluting substances in comparison to DBD and the Fentonprocess (about 80%). After all treatments, by analysis of mass spectra 12 degradationproducts of ibuprofen were identified: five aromatic and seven aliphatic products. In thesolution after the DBD/Fe2+treatment only 4 aliphatic carboxylic acids were detected.Ecotoxicological effect of the ibuprofen solution treated in the DBD reactor as well as inthe DBD/Fe2+ system was not detected. In relation to A.salina, V. fischeri has shown greatersensitivity to degradation products which appeared during the Fenton treatment. The toxiceffect of ibuprofen solution after the Fenton treatment was categorized as class III, that is"Toxic".The highest degradation percentage of ibuprofen was achieved by application ofEAOPs in the Pt - Pd system (98%), with the current of 100 mA and at the pH value of 3.The toxic effect expressed as the mortality (%) of A. saline was less than 30% at the highesttested concentration 100% (c, v/v) of ibuprofen solution treated in the Pt-Pd system. TheV.fischeri was the more sensitive model for the assessment of the ibuprofen degradationproducts toxic effect after the Pt-Pd treatment in comparison to A.salina.

Ovaj završni rad govori o arsenu. Možemo ga podijeliti na tri dijela. Prvi dio govori o arsenu kao elementu, njegovim nalazištima, dobivanju, upotrebi i povijesti. Drugi dio govori o problematici industrije i teških metala, s naglaskom na tekstilnu industriju. Treći dio rada govori o arsenovim spojevima, njegovoj prisutnosti u okolišu, hrani i vodi za piće te njegovim štetnim učincima za ljudsko zdravlje.

U ovom je radu iznesen pregled najnovijih ihtioloških istraživanja u kojima se autori služe tzv. mikronukleusnim testom. Test se u znanstvenoj literaturi spominje već čitav niz godina kao jedno od osnovnih sredstava za utvrđivanje oštećenja na DNK organizma–modela. Znanstvenici se njime koriste radi dokazivanja genotoksičnih utjecaja različitih tvari na organizme, u ovom slučaju hidrobionte., The purpose of this paper was to give an insight into the most recent ichthiology research in which Micronucleus test is used. This test has been used for some time now as a tool for determining DNA damage in model–organism. Scientists have been using it in order to assess genotoxic effects which certain substancies exhibit towards different organisms, in this case hydrobionts.

V magistrski nalogi smo želeli ugotoviti, kakšen je vpliv dezinfekcijskega sredstva (kvarterne amonijeve spojine benzalkonijev klorid (BAC)) na enocelično sladkovodno algo Pseudokirchneriella subcapitata. BAC se uporablja kot dezinfekcijsko sredstvo ter je prisoten v številnih drugih proizvodih, njegova svetovna letna poraba pa se ocenjuje na 500.000 ton (CESIO, 2004). Zabeležene koncentracije v okolju so med 0,2 in 3,0 µg/L (Martinez-Carballo et al, 2007a,b). V okolju pride BAC v stik z vodnimi organizmi. Preučevali smo njegov vpliv na algo Pseudokirchneriella subcapitata, saj so primarni producenti temelj prehranjevalne verige, zato bi lahko imele spremembe v tej združbi vpliv na celoten ekosistem. Eksperimentalni del smo izvedli v skladu z navodili OECD TG 201 (2011). Ugotovili smo, da je BAC v koncentracijah nad 0,052 mg/L (EC20) toksičen za to algo, saj povzroči statistično značilno inhibicijo rasti alge. Z višanjem koncentracije BAC nad to vrednostjo se je sigmoidno povečevala stopnja inhibicije rasti. V naravi so snovi po navadi prisotne v mešanicah, zato smo si izbrali BAC kot modelno dezinfekcijsko sredstvo in 5-FU kot modelno protirakavo zdravilo. Protirakavo zdravilo 5-FU je namreč eno izmed najpogosteje uporabljanih zdravil za zdravljenje rakavih obolenj in se najpogosteje aplicira v bolnišnicah (Kovalova, 2009). Kot dezinfekcijsko sredstvo za površine se v bolnišnicah pogosto uporablja BAC (Kümmerer, 2001), zato se pričakuje, da je v bolnišničnih iztokih in posledično tudi v okolju, prisotna mešanica BAC in 5-FU. Ugotovili smo, da je mešanice teh dveh snovi za izbrano algo bolj toksična od posameznih komponent, razen v primeru BAC pri vrednosti EC90, pri kateri je bila toksičnost za algo višja kot pa v mešanici s 5-FU. Učinek mešanice 5-FU in BAC smo primerjali z oceno toksičnosti mešanic, ki jo podajata dva matematična modela, model seštevka koncentracij in model neodvisnega delovanja. Ugotovili smo, da noben izmed modelov ne poda pravilne ocene toksičnosti za to mešanico pri koncentracijah nad EC20, saj so eksperimentalni rezultati po 72 urah pokazali višjo toksičnost mešanice za P. subcapitata, kot pa jo predvidevata uporabljena modela. Dobljeni rezultati so pokazali, da BAC pri koncentracijah, ki so prisotne v okolju lahko vpliva na alge. Zmes BAC in 5-FU pri koncentracijah ugotovljenih v bolnišničnih odpadnih vodah zaradi sinergističnega delovanja predstavlja večje tveganje za alge kot posamezna snov. The goal of the present study was to investigate the effects of a disinfectant (a quaternary ammonium compound benzalkonium chloride (BAC)) on the fresh-water microalgae Pseudokirchneriella subcapiata. BAC is used as a disinfection agent and is present in many commercially available products. The estimation of its annual consumption is 500000 tons (CESIO, 2004). The measured concentrations of BAC in the environment were between 0,2 and 3,0 µg/L (Martinez-Carballo et al, 2007a,b). Once in the environment, BAC comes in contact with aquatic organisms. We investigated its effect on algae Pseudokirchneriella subcapitata, as primary producers in aquatic systems are the base of the food chain, and therefore changes in their community could affect the whole ecosystem. The experimental part was preformed according to OECD TG 201 (2011) standards. The results showed that BAC is toxic to the investigated algae at concentrations above 0,052 mg/L (EC20), at which it causes statistically significant inhibition of growth rate. Higher concentrations of BAC caused a sigmoid increase of growth rate inhibition. In the environment substances are usually found in mixtures, so we chose BAC as a model disinfection agent and 5-FU as model anti-cancer drug. The anti-cancer drug 5-FU is one of the most commonly used cytostatic drugs (Kovalova, 2009) and is usually applied in hospitals. BAC is commonly used in hospitals as surfactant (Kümmerer, 2001), therefore it is expected that the mixture of BAC and 5-FU is present in hospital wastewaters as well as in the environment. The measured toxicity of the mixture of those substances was higher to the selected algae than when those substances were applied individually, except in the case of BAC at concentration of EC90, at which the toxicity of the single compound was greater than the mixture. The experimentally determined toxicity of the mixture of 5-FU and BAC was compared to the prediction of mixture toxicity using the mathematical models of 'concentration addition' and 'independent action'. The results showed that none of the models used can accurately predict the toxicity of the selected mixture at concentrations above EC20, as the experimental data showed higher toxicity to the selected algae after a 72 hour exposure than that predicted by the models. Our results show that BAC affects the algae at concentrations present in the environment. The mixture of BAC and 5-FU at concentrations measured in hospital wastewaters represents a higher risk for algae than as single compounds do, as these compounds show a synergistic effect.

Ionske kapljevine su organske soli niskog tališta sastavljene u cijelosti od iona. Zbog svojih specifičnih svojstava, predstavljaju moguću i dobru zamjenu za organska otapala koja imaju negativan učinak na okoliš i ljude. Obzirom na svojstva, strukturu i vrijeme otkrivanja ionske kapljevine dijele se na ionske kapljevine prve, druge i treće generacije. Prirodne ionske kapljevine pripadaju četvrtoj generaciji i one su ekološki i ekonomski najprihvatljivije. U ovom radu ispitan je utjecaj šest kolinijevih ionskih kapljevina na preživljenje CCO stanične linije riba WST-1 metodom. Na temelju dobivenih rezultata, ispitane ionske kapljevine u usporedbi s ionskim kapljevinama prethodnih generacija pokazale su manju citotoksičnost na CCO stanicama te time i bolji ekotoksikološki profil.