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Kot posledica 360 letne zgodovine rudarske dejavnosti v Zgornji Mežiški dolini, so tla močno onesnažena s kadmijem (Cd) in svincem (Pb). Na območjih velike onesnaženosti imajo lokalni prebivalci pogosto vrtove za lastno pridelavo vrtnin. Rastline kovine sprejemajo iz tal in jih kopičijo v užitnih delih. Tako kovine prehajajo v prehranjevalno verigo človeka. Z različnimi dodatki tlem lahko zmanjšamo biodostopnost potencialno toksičnih onesnažil za žive organizme. V pilotni raziskavi smo želeli ugotoviti ali imajo dodatki, ki smo jih izbrali na podlagi predhodnih študij, učinek na mobilnost in biološko dostopnost izbranih kovin ter raziskati možnosti njihove nadaljnje uporabe za sanacijo onesnaženih tal. V lončnem poskusu z rdečo peso (Beta vulgaris L.) smo testirali pet različnih dodatkov tlem, z namenom ugotoviti razlike v akumulaciji Cd in Pb v nadzemnih in podzemnih delih izbrane rastline. Izbrali smo biooglje, zeolit, papirniški mulj, kompost in vermikulit. Pripravili smo mešanice onesnaženih tal iz Žerjava in izbranih dodatkov. Dodatki tlem niso uspeli zmanjšati prenosa Pb ali Cd iz onesnaženih tal v rdečo peso pod mejno vrednost za živila. Pri svincu si to lahko razlagamo preko prvotno majhne biodostopnosti in mobilnosti kovine glede na njegovo veliko skupno vsebnost, kar lahko delno pripišemo lastnostim samega elementa. Kadmij je bolj dostopen element, na njegovo biodostopnost vpliva pH in velika skupna vsebnost, zato izmenljive frakcije niso uspeli bistveno zmanjšati z dodatki. The result of the 360-year history of mining activity in the Upper Meža valley is soil heavily contaminated with cadmium (Cd) and lead (Pb). In areas of high pollution, local residents often have gardens. Heavy metals accumulate in the edible parts of vegetables and thus enter the human food chain. With various amendments, we can potentially reduce the bioavailability of toxic pollutants to living organisms. In the pilot study, we wanted to determine whether the amendments we selected on the basis of previous studies have an effect on the mobility and bioavailability of certain heavy metals, and to investigate the possibilities of their further use for the remediation of contaminated soils. In a pot experiment with beetroot (Beta vulgaris L.), five different soil additives were tested in order to determine the differences in the accumulation of Cd and Pb in the above-ground and underground parts of the selected plant. We chose biochar, zeolite, paper mill sludge, compost and vermiculite. We prepared mixtures of contaminated soil and selected additives. Soil amendments failed to reduce the transfer of Pb or Cd from contaminated soils to beetroot below the threshold value. In the case of lead, this can be explained through originally low bioavailability and mobility in relation to its high total content, which can be partially attributed to the properties of the element itself. We believe that pH may be responsible for the maximum concentration of the exchangeable fraction of cadmium.

The aim of the study was to investigate the effects of chitosan oligosaccharide (COS) on some hematological parameters, and define the percentage of alpha-naphthyl acetate esterase (ANAE) positive lymphocytes in rats that had been exposed to cadmium (Cd). Thirty-two (n = 32) male Wistar albino rats were randomly divided into four groups as the control (C), chitosan oligosaccharide (COS), cadmium (Cd), and Cd + COS (CdCOS) groups. Blood samples were collected to assess erythrocytes (RBC), leukocytes (WBC), hemoglobin levels (HGB), hematocrit values (HCT), mean corpuscular hemoglobin (MCH), mean corpuscular hemoglobin concentration (MCHC), mean corpuscular volume (MCV), platelets (PLT), and alpha-naphthyl acetate esterase (ANAE) positive lymphocytes. The number of WBCs significantly increased in the Cd group compared to the C, CdCOS, and COS groups (P, Cilj ovog rada bio je istražiti učinak oligosaharida hitozana (COS) na određene hematološke pokazatelje odnosno postotak limfocita pozitivnih na alfa-naftil-acetat-esterazu (ANAE) u štakora izloženih kadmiju (Cd). Mužjaci (n = 32) pasmine Wistar albino, slučajnim odabirom podijeljeni su u četiri skupine: kontrolnu (C), skupinu s oligosaharidom hitozanom (COS), skupinu s kadmijem (Cd) i skupinu s kadmijem i oligosaharidom hitozanom (CdCOS). Prikupljeni su uzorci krvi kako bi se odredili eritrociti (RBC), leukociti (WBC), hemoglobin (HGB), hematokrit (HCT), prosječni hemoglobin u eritrocitima (MCH) i njegova koncentracija (MCHC), prosječan obujam eritrocita (MCV), trombociti (PLT), te limfociti pozitivni na alfa-naftil-acetat-esterazu (ANAE). Broj leukocita znakovito je porastao u skupini Cd u usporedbi s kontrolnom skupinom te skupinama C, CdCOS, i COS (P < 0,05). Iako je broj limfocita znakovito smanjen u skupini Cd (P < 0,05), to je ublaženo primjenom COS-a u skupini CdCOS u usporedbi sa skupinom Cd (P < 0,05). Također, postotak limfocita iz periferne krvi pozitivnih na ANAE znakovito je smanjen u skupinama CdCOS i Cd (P < 0,05). COS je, u slučaju kronične izloženosti štakora kadmiju, pokazao djelomice zaštitni učinak na određene hematološke značajke, osim na postotak limfocita pozitivnih na ANAE.

Ispitano je vezanje iona žive i kadmija na prirodnom zeolitu u prisustvu otopina Humistar ® i Fertireg ® koji su dodaci tlu u poljoprivredi. Utvrđen je veći stupanj uklanjanja iona žive i kadmija pri nižim početnim koncentracijama kao i niža količina iona vezana po gramu zeolita. Dodatak otopina Humistar ® i Fertireg ® ne utječe na stupanj uklanjanja žive kao i na količinu vezane žive po gramu zeolita. Utvrđeno je povećanje stupnja uklanjanja kadmija uz dodatak otopina Humistar ® i Fertireg ® i to je povećanje više izraženo uz veće koncentracije organske tvari. Također, količina vezanog kadmija po gramu zeolita raste uz dodatak otopina Humistar ® i Fertireg ® te se može zaključiti da organska tvar pozitivno utječe na remedijaciju tla onečišćenog kadmijem, dok na remedijaciju tla onečišćenog živom nema utjecaja pri ispitanim koncentracijama. The binding of mercury and cadmium ions on natural zeolite has been examined in the presence of Humistar ® and Fertireg ® solutions, which are soil additives in agriculture. A higher degree of removal of mercury and cadmium ions at lower initial concentrations was determined, as well as a lower amount of bound ions per gram of zeolite. The addition of Humistar ® and Fertireg ® solutions does not affect the efficiency of mercury removal as well as the amount of bound mercury per gram of zeolite. An increase in removal efficiency of cadmium is observed with the addition of Humistar ® and Fertireg ® solutions, and this increase is more pronounced with higher concentrations of organic matter. Also, the amount of bound cadmium per gram of zeolite increases with the addition of Humistar ® and Fertireg ® solutions, and it can be concluded that organic matter has a positive effect on the remediation of cadmium soil contaminated, while remediation of mercury soil contaminated has no effect at the examined concentrations.

Mikroplastika so plastični delci manjši od 1 mm, ki jih lahko najdemo v zraku, vodi, zemlji in sedimentih, v zelo različnih oblikah, barvah in kemijskih sestavah. Mikroplastika v naravnem okolju adsorbira in akumulira različna onesnaževala, kot so obstojna organska onesnaževala in kovine. Koncentracije onesnaževal na mikroplastiki so lahko tudi od 10 do 100-krat višje od tistih, ki jih najdemo v okolju. V magistrskem delu smo se osredotočili na adsorpcijo kovin na mikroplastiko. Najprej smo preiskovali adsorpcijo kovin iz odpadne vode na mikroplastiko pridobljeno iz kozmetičnih izdelkov. To mikroplastiko smo tudi okarakterizirali s pomočjo analize porazdelitve velikosti delcev in s SEM/EDS analizo. V drugem delu smo adsorbirali kadmij na mikroplastiko, ki je bila obraščena z biofilmom in je tako najbolj podobna mikroplastiki v okolju. Ugotovili smo, da je adsorpcija kadmija bistveno višja na mikroplastiki obdani z biofilmom, kot na mikroplastiki brez biofilma. Microplastics are small plastic pieces up to one millimetre long. They can be found in air, water, soil and sediments in different shapes, colours and chemical compositions. Microplastics in the environment can adsorb and accumulate different pollutants, such as pharmaceuticals, persistent organic pollutants and metals. Concentrations of pollutants accumulated on such particles can be 10–100 times higher than the concentrations in the surrounding environment. The aim of the master's thesis was to evaluate if metals can be adsorbed onto microplastics. We first investigated the adsorption of metals from wastewater onto microplastics, which are obtained from cosmetic products. The morphological properties of this microplastic were characterized by particle size distribution analysis and SEM/EDS analysis. In the second part, we verified the adsorption of cadmium onto microplastics with biofilm, which are the most similar to microplastics in the environment. Adsorption of cadmium is significantly higher on microplastics with biofilm, than on microplastics without it.

Z napredkom industrializacije in sorazmerno rastjo onesnaževanja okolja je razvoj metod, ki bi omejile kopičenje težkih kovin v rastlinah in v prehranjevalni verigi, vse bolj pomemben. V primeru onesnaženja s kadmijem (Cd), je ena izmed potencialno uporabnih metod gnojenje rastlin s cinkovim sulfatom (ZnSO4). Namen raziskave je bil izmeriti koncentracijo Cd v rastlinskih tkivih česna (Allium sativum L.) in oceniti razlike med privzemom Cd pri štirih komercialno dostopnimi kultivarji. Cilj je bil tudi preučiti vpliv gnojenja s ZnSO4 na privzem Cd in koncentracijo cinka (Zn) v česnu. Iz štirih kultivarjev, ki so uspevali na polju, smo vzorčili po pet rastlin z rizosferno zemljo za vsak kultivar in vsako obravnavo. S pomočjo induktivno sklopljeno plazmo masnega spektrometra (ICP-MS) smo v posušenih, uprašenih in homogeniziranih tkivih (korenine, listi in stroki) po kislinskem razklopu izmerili koncentracijo Zn, Cd in žvepla (S). Izmerili smo tudi koncentracijo dostopnega Zn in Cd v rizosferni zemlje, ki smo jo pridobili z ekstrakcijo z amonijevim acetatom. Rezultati so pokazali, da je najvišja koncentracija Cd v koreninah, sledijo stroki in nato listi. Pokazali smo statistično značilne razlike v koncentraciji Cd v strokih med proučevanimi kultivarji česna. Gnojenje s ZnSO4 je pokazalo trend upadanja koncentracije Cd v stroku, vpliva na koncentracijo Zn v strokih pa nismo opazili. Gnojenje s ZnSO4 se je izkazalo za izvedljivo agronomsko metodo pri nadzoru privzema Cd. With the development of industrialization and subsequent pollution, there is increasing need to develop methods that would limit the accumulation of heavy metals in plants and therefore in the foodchain. In case of cadmium (Cd) pollution, one of potentially useful methods may be fertilisation of plants with zinc sulphate (ZnSO4). The purpose of the study was to measure the concentration of Cd in plant tissues of garlic (Allium sativum L.) and to evaluate differences between Cd uptake between four commercially available cultivars. In addition, the effect of fertilization with ZnSO4 on Cd and zinc (Zn) concentration in garlic was determined. For each of the four cultivars and for each treatment five plants with rhizosphere soil were sampled in the field, where plants were cultivated. Dried, milled and homogenised samples (roots, leaves and cloves) were wet digested and concentrations of Cd, Zn and sulphur (S) were measured using inductively coupled plasma mass spectrometry (ICP-MS). The available fractions of Zn and Cd were extracted from rhizosphere soil with ammonium acetate and their concentrations measured with ICP-MS. The highest concentration of Cd was measured in the roots, then in the cloves and the least in the leaves. There was significant difference in Cd concentrations in cloves between cultivars. Fertilization with ZnSO4 showed a declining trend in the concentration of Cd in the cloves, but there was no significant effect on the concentration of Zn in the cloves. ZnSO4 fertilization has proven to be a viable agronomic method in the control of Cd uptake.

Elektrokemijske tehnike so v primerjavi s spektroskopskimi in kromatografskimi metodami manj zapletene za uporabo in zanje običajno ni potrebna kompleksnejša obdelava vzorca pred meritvijo. Številne celo omogočajo in situ meritve – torej brez vzorčenja, kar je pri okoljski analizi zelo priročno za kontinuirni monitoring onesnažil v pretočnem sistemu kot je reka, morje ipd. Ena od elektrokemijskih tehnik, ki je primerna za določanje sledov kovin, je anodna inverzna (stripping) voltametrija, ki se je razvila v prejšnjem stoletju. V zadnjih 60 letih so se za takšne meritve najpogosteje uporabljale različne oblike živosrebrovih elektrod (kapljajoča, viseča, tankoplastna elektroda itd.), ki so okolju in živim organizmom škodljive, težavo pa predstavlja tudi rokovanje z živim srebrom, njegova hramba, itd. V mnogih državah je uporaba živega srebra močno omejena ali celo prepovedana. Kot nadomestek za živo srebro kot elektrodni material so bili preizkušeni mnogi prevodni materiali, kot so različne oblike prevodnega ogljika (pirolitski grafit, polikristalinični grafit, elektroda iz ogljikove paste, steklasti ogljik, ogljikova vlakna), zlato, platina, srebro, iridij, itd., toda nobeden od naštetih ni dosegel izjemnih elektroanaliznih karakteristik živosrebrovih elektrod. Leta 2000 je skupina iz Odseka za analizno kemijo (Kemijski Inštitut) v sodelovanju z ameriškim partnerjem (Department of Chemistry and Biochemistry, New Mexico State University, Las Cruces) vpeljala uporabo bizmuta za stripping voltametrično detekcijo izbranih sledov ionov težkih kovin. Temu je v letu 2006 sledila predstavitev tankoslojne antimonove elektrode, nedavno pa so na Odseku za analizno kemijo študirali tudi zanimivo uporabo tankoslojne bakrove elektrode za detekcijo nekaterih ionov težkih kovin v sledovih. V pričujočem magistrskem delu je predstavljena raziskava elektrokemijskih lastnosti in uporabe različnih bakrovih elektrod za določitev nizkih koncentracij Pb2+ in Cd2+ v vodnih medijih z anodno inverzno (stripping) voltametrijo. Pri svojem delu sem obravnaval tako tankoslojne bakrove elektrode, pripravljene na osnovni elektrodi iz steklastega ogljika in tiskani ogljikovi elektrodi, kot tudi trdne bakrove elektrode (trdna bakrova (disk) elektroda, tiskana bakrova elektroda in bakrova žica). Preučeval sem vplive različnih parametrov, kot so sestava medija, koncentracija bakrovih(II) ionov, čas depozicije bakra in analitov ter napetost depozicije, na stabilnost in občutljivost elektrode ter jih skušal optimizirati. Preučeval sem tudi območje linearnosti, ponovljivost meritev, spodnjo mejo zaznave (LOD) ter spodnjo mejo kvantifikacije (LOQ) za posamezno obravnavano elektrodo. Izkazalo se je, da imajo bakrove elektrode precej podobne lastnosti nekaterim že uveljavljenim in razširjenim kovinskim elektrodam, kot sta na primer antimonova in bizmutova elektroda. Odlikuje jih relativno visoka občutljivost in zato ugodno nizek LOD, dobra ponovljivost ter široko linearno koncentracijsko območje delovanja. Baker je kot elektrodni material poceni in zaradi svojih lastnosti (večina njegovih spojin je relativno nestrupenih za organizme – uporablja se celo za pospeševanje rasti pri reji prašičev) neproblematičen za uporabo. Electrochemical techniques are much less complicated for use compared to spectroscopic and chromatographic methods – sample preparation is usually not required. Many of them allow in situ determination, which is important in environmental analysis for continuous monitoring of contaminant concentrations in flow systems such as rivers and oceans. Anodic stripping voltammetry is one of the electrochemical techniques that developed in the late 20th century for the analysis of trace metals. In the last 60 years, different mercury electrodes (dropping mercury electrode – DME, hanging mercury dropping electrode – HDME, mercury film electrode – MFE) have been used for this kind of measurements, which are dangerous for the environment and living organisms. There is also a problem with handling and storage of mercury. Today, the use of mercury is restricted or even banned. Many electrically conductive materials such as various forms of electrically conductive carbon (pyrolytic graphite – PG, polycrystalline graphite, carbon paste electrode – CPE, glassy carbon electrode – GCE, carbon fibres, etc.), gold, platinum, silver, iridium, etc. have been used to replace mercury as electrode materials, but none of them exhibited excellent electroanalytical properties of mercury electrodes. In 2000, a group of scientists from the Department of Analytical Chemistry (National Institute of Chemistry, Ljubljana) in collaboration with an American partner institution (Department of Chemistry and Biochemistry, New Mexico State University, Las Cruces) introduced bismuth in stripping voltammetry measurements for the detection of heavy metal traces. Then, in 2006, the antimony film electrode was introduced. Recently, the use of copper film electrodes for the detection of selected heavy metal ion traces was investigated by the Department of Analytical Chemistry. This master’s thesis represents an investigation of properties and applications of various copper electrodes for determination of lead(II) and cadmium(II) ions in low concentrations in water solutions using anodic stripping voltammetry. In my work, copper-film electrodes based on glassy carbon electrodes and screen-printed electrodes (SPE) with carbon working electrode as well as bulk copper electrodes (copper disc electrode, SPE with copper working electrode, copper wire) were investigated. I investigated the influences of various parameters such as medium, copper(II) concentration, time of deposition of copper and analytes and deposition potential on the stability and sensitivity of the electrodes. In the next phase, the parameters were optimised to obtain the best performance of the electrodes, and then their range with linear response, repeatability and limits of detection and quantification (LOD, LOQ) were determined. The experiments have shown that copper electrodes are very similar to some other already established metal electrodes, for example, antimony and bismuth electrodes. They have good sensitivity and therefore a low detection limit, as well as good repeatability and a broad linear response. Copper as an electrode material is inexpensive and, due to its qualities (the toxicity of most its compounds to organisms is relatively low – it is even used as growth promoter in breeding pigs), it is not problematic to use.

This study deals with the biomonitoring of cadmium (Cd) heavy metal in the three selected Tricholoma mushroom species collected from wild habitats of central and coastal Croatia. For this, mushroom (T. columbetta: n = 38, T. portentosum: n = 35, and T. terreum: n = 34) and surface soil samples were collected from nine forest localities of Croatia and analyzed for Cd concentration using inductively coupled plasma–optical emission spectrometry (ICP–OES) through the acid digestion method. The findings revealed that Cd was present in Tricholoma spp. and surface soil. However, the maximum mean Cd concentration (mg/kg dry weight) was recorded in T. portentosum (cap: 0.98; stipe: 0.72), followed by T. columbetta (cap: 0.96; stipe: 0.73) and T. terreum (cap: 0.81; stipe: 0.63). The bioconcentration factor (BCF) value (>1) revealed that the selected Tricholoma spp. had the potential for Cd accumulation. Moreover, the principal component (PC) and hierarchical cluster (HC) analyses were used to derive the interactions and similarities between Cd levels Tricholoma spp. and sampling localities. The multivariate analysis suggested that central sampling localities had higher Cd levels as compared to coastal localities. However, the daily intake of metals (DIM < 0.426) and health risk index (HRI < 1) showed that there was no potential health risk associated with the consumption of selected Tricholoma spp. The findings of this study are helpful to understand the Cd accumulation behavior of wild edible Tricholoma spp. collected from Croatia.

Paper-ash is used for remediation of heavily contaminated soils with metals, but remediation efficiency after longer periods has not been reported. To gain insights into the mechanisms of immobilization of cadmium (Cd), lead (Pb), and znic (Zn), a study was performed in the laboratory experiment in uncontaminated, artificially contaminated, and remediated soils, and these soils treated with sulfate, to mimic conditions in contaminated soil from zinc smelter site. Remediation was performed by mixing contaminated soil with paper-ash to immobilize Cd, Pb, and Zn in the geotechnical composite. Partitioning of Cd, Pb, and Zn was studied over one year in seven-time intervals applying the sequential extraction procedure and complementary X-ray diffraction analyses. This methodological approach enabled us to follow the redistribution of Cd, Pb, and Zn over time, thus, to studying immobilization mechanisms and assessing the remediation efficiency and stability of newly formed mineral phases. Cd, Pb, and Zn were effectively immobilized by precipitation of insoluble hydroxides after the addition of paper-ash and by the carbonization process in insoluble carbonate minerals. After remediation, Cd, Pb, and Zn concentrations in the water-soluble fraction were well below the limiting values for inertness: Cd by 100 times, Pb by 125 times, and Zn by 10 times. Sulfate treatment did not influence the remediation efficiency. Experimental data confirmed the high remediation efficiency and stability of insoluble Cd, Pb, and Zn mineral phases in geotechnical composites. Nasl. z nasl. zaslona. Opis vira z dne 14. 12. 2021. Št. članka 11822. Bibliografija: str. 13-15. Abstract.

Pričujoče magistrsko delo obsega študijo odstranjevanja svinca, cinka in kadmija iz vzorčenih sedimentov s postopkom spiranja sedimenta. Vzorčenje sedimenta je bilo izvedeno ob reki Dravi (severni del Ptujskega jezera). Odvzeta sta bila dva sedimenta: sediment S (star), ki je bil na obalo prečrpan pred 15 leti in sediment N (nov), prečrpan pred 1 letom. V ta namen je bil sediment okarakteriziran z vrsto analiz: določeni so bili delež vode (S 4,5 % in N 8,9 %), delež žaroizgube (S 12,6 % in N 10,8 %), z uporabo kislinskega razklopa z dušikovo(V) kislino pa so bili določeni celokupni deleži svinca (pribl. 400 ppm), cinka (pribl. 1100 ppm) in kadmija (pribl. 7 ppm). Prav tako so bili ti deleži določeni v vzorcu sedimenta, ki je bil ločen v velikostne frakcije. Ugotovljeno je bilo, da se z manjšanjem velikosti delcev povečuje delež težkih kovin. Izvedene so bile analize učinkovitosti spiranja sedimenta z različni reagenti: HNO3, HCl, EDTA, citronsko kislino, huminsko kislino, ramnolipidom, saponinom, DL-mlečno, salicilno, L-askorbinsko, jantarno, DL-jabolčno, L-vinsko in ocetno kislino. Pri spiranju sedimenta s tremi reagenti, ki so se najbolje izkazali (EDTA, citronska kislina in DL-jabolčna kislina) je bila opravljena optimizacija treh pogojev spiranja: koncentracije reagenta, časa oz. trajanja spiranja in razmerja med volumnom izpiralne raztopine in maso sedimenta [mL/g] (razmerje R/S). preizkušeno je bilo tudi dvakratno zaporedno spiranje sedimenta. Vse meritve za kvantitativno določitev svinca, cinka in kadmija so bile opravljene z uporabo plamenske atomske absorpcijske spektroskopije (FAAS). Ugotovljeno je bilo, da so vsi uporabljeni reagenti v določeni meri sposobni odstraniti svinec, cink in kadmij iz sedimenta. Najuspešnejši pri tem so bili EDTA (delež odstranjene kovine: Pb 40 %, Zn 15 % in Cd 55 %), citronska kislina (delež odstranjene kovine: Pb 50 %, Zn 60 % in Cd 75%) in DL-jabolčna kislina (delež odstranjene kovine: Pb 45 %, Zn 60 % in Cd 75 %), Slednji sta pri določenih pogojih za vse kovine presegli učinkovitost EDTA. Z optimizacijo spiranja sedimenta s temi reagenti je bil preverjen vpliv pogojev na njihovo učinkovitost odstranjevanja kovin. Določeni so bili optimizirani pogoji za te reagente: EDTA 0,01 M, 16 h in R/S = 5/1 citronska kislina 0,2 M, 16 h in R/S = 10/1 DL-jabolčna kislina 0,3 M, 16 h in R/S = 10/1. S citronsko kislino in z DL-jabolčno kislino izvedeno dvakratno zaporedno spiranje sedimenta je doseglo še višjo učinkovitost odstranjevanja kovin kot optimizirano spiranje. Spiranje sedimenta z različnimi reagenti se je na laboratorijski skali izkazalo za uporaben postopek za odstranjevanje svinca, cinka in kadmija. Nadaljnje raziskave bodo vključevale: frakcionacijsko analizo sedimenta (v kakšni obliki so kovine prisotne), preizkus kombinacij uporabljenih reagentov in uporaba novih (fitinska kislina oz. fitati), apliciranje razvitih postopkov spiranja na certificirane referenčne materiale (CRM) in druge vrste sedimentov ter možnosti predelave izlužene raztopine, ki po spiranju vsebuje visoke koncentracije težkih kovin. The following dissertation contains a study of the removal of lead, zinc, and cadmium from sampled sediments using a process known as sediment washing. Sediment samples were collected near the Drava River (north side of Lake Ptuj). Two sediment samples were taken: sediment S (old), dredged from the river 15 years ago, and sediment N (new), dredged one year ago. A series of analyses were performed: sediment was characterized by determining water content (S 4.5 % and N 8.9 %) and loss on ignition (LOI) (S 12.6 % and N 10.8 %). Total metal content of lead, zinc, and cadmium was determined by means of acid digestion of the sediment with nitric(V) acid. The approximate values are 400 ppm for lead, 1100 ppm for zinc and 7 ppm for Cd. The same was done for a sediment sample, which was separated by particle size. It was observed that the heavy metal content increases with decreasing particle size. Analyses of metal removal effectiveness were performed using various chemical reagents: HNO3, HCl, citric acid, humic acid, rhamnolipid, saponin, DL-lactic acid, salicylic acid, L-ascorbic acid, succinic acid, DL-malic acid, tartaric acid, and acetic acid. Sediment washing with EDTA, citric acid, and DL-malic acid was optimized. The conditions that were optimized were the concentration the of reagent, the washing time and the ratio between the volume of the washing solution and the mass of the sediment (R/S ratio). Sediment washing with two successive washing cycles was also investigated. All measurements used for the quantification of lead, zinc, and cadmium were done by flame atomic absorption spectroscopy (FAAS). It was found that all reagents tested were able to remove lead, zinc, and cadmium from the sediment to some degree. EDTA (percentage of metals removed: Pb 40 %, Zn 15 % and Cd 55 %), citric acid (percentage of metals removed: Pb 50 %, Zn 60 % and Cd 75 %), and DL-malic acid (percentage of metals removed: Pb 45 %, Zn 60 % and Cd 75 %) proved to be the most successful. Under certain conditions, the two simple carboxylic acids removed even more of the metals than EDTA. For all three reagents, the dependence of their effectiveness of metal removal on sediment washing conditions was investigated by optimizing the procedure. The optimal conditions were also determined for these reagents: EDTA concentration 0.01 M, washing time 16 h and ratio R/S = 5/1 citric acid 0.2 M, 16 h and R/S = 10/1 DL-malic acid 0.3 M, 16 h and R/S = 10/1. Sediment washing with two successive washing cycles was carried out with citric acid and DL-malic acid and proved to be more effective in removing metals than sediment washing under optimized conditions. At laboratory scale, the sediment washing process using different chemical reagents was demonstrated to be effective at removing lead, zinc, and cadmium. Further work will include: speciation of present metals by fractional analysis of the sediment, using a combination of two or more reagents for sediment washing, testing new reagents for sediment washing (phytic acid and phytates), applying the developed sediment washing procedures to CRM materials and other sediment types, and possible remediation of the leaching solution, which contains high concentrations of heavy metals after sediment washing.

Ispitana je mogućnost primjene prirodnog zeolita klinoptilolita kao punila u propusnim reaktivnim barijerama (PRB) za zaštitu podzemnih voda od onečišćenja teškim metalima. Za simuliranje dinamičkih uvjeta u podzemlju provedeni su eksperimenti u koloni na nepomičnom sloju prirodnog zeolita klinoptilolita propuštanjem binarne vodene otopine kadmija i cinka od vrha prema dnu kolone pri protocima od 1, 2, 3 i 4 mL/min. Iz dobivenih eksperimentalnih rezultata izračunati su koeficijent raspodjele (K d ) i koeficijent zadržavanja (R d ), kako bi se procijenio potencijal zeolita za sorpciju i zadržavanje kadmija i cinka u barijeri. Također su izračunati hidrodinamički koeficijent disperzije (D L ) i hidrodinamički disperzijski koeficijent zadržavanja (D LR ) u svrhu procjene utjecaja hidrodinamičke disperzije na širenje onečišćenja u podzemnoj vodi i zaobilaženje postavljenje barijere. Za sve ispitane protoke dobivene su veće vrijednosti K d i R d za kadmij nego za cink što upućuje na bolju raspodjelu i zadržavanje kadmija u sloju zeolita. Razlog tome je njegov manji hidratizirani ionski radijus u odnosu na cink, što mu omogućuje bolju pokretljivost, a time i vezanje na slobodna aktivna mjesta na zeolitu. Povećanjem protoka manja je razlika između K d i R d za kadmij i cink jer je uslijed kraćeg vremena kontakta kompeticijski efekt između kadmija i cinka manje izražen. Vrijednosti D L i D LR za oba iona rastu porastom protoka, povećavajući njihovo širenje u poroznom mediju uslijed hidrodinamičke disperzije, što u konačnici može dovesti do zaobilaženja postavljene barijere. Najbolja raspodjela i zadržavanje iona u zeolitnoj barijeri uz njihovo minimalno širenje postignuta je za najmanji protok otopine od 1 mL/min (0,01277 m/min) koji je od svih ispitanih protoka najbliži prosječnom protoku podzemne vode (≈ 0,00003 m/min). Dobiveni rezultati ukazuju na mogućnost primjene prirodnog zeolita klinoptilolita kao punila u propusnim reaktivnim barijerama u svrhu zaštite podzemnih voda od onečišćenja teškim metalima. The possible application of natural zeolite clinoptilolite as filler in permeable reactive barriers (PRBs) for protection of groundwater from contamination by heavy metals were investigated. For simulation of underground dynamic conditions for the column experiments on the fixed natural zeolite layer were performed by passing the binary aqueous solution of cadmium and zinc through the column by down-flow mode at flow rates of 1, 2, 3 and 4 mL/min. From the obtained column results the distribution coefficient (K d ) and retardation coefficients (R d ) were calculated in order to estimate the zeolite potential in sorption and retardation of cadmium and zinc in the barrier. The hydrodynamic dispersion coefficient (D L ) and hydrodynamic dispersion retardation coefficient (D LR ) were calculated as well in order to estimate the impact of the hydrodynamic dispersion on the contaminant plume and possible bypassing of the barrier. For all flow rates tested, the highest values of K d and R d were obtained for cadmium compared to zinc, pointing on better distribution and retardation od cadmium in zeolite layer. The reason for that is smaller hydrated ionic radius of cadmium than zinc, making it more mobile, and thus easier to bind on free active zeolite sites. With increasing in flow rate the difference between the K d and R d of cadmium and zinc is lower due to the shorter contact time at which to competition effect is less pronounced. The D L and D LR values for both ions increase with increasing in flow rate, thus increasing their spreading in the porous media caused by hydrodynamic dispersion, which at the end leads to bypassing of the barrier. The best distribution and immobilization of the ions inside the zeolite barrier, alongside their minimum spreading is achieved for the lowest flow rate of 1 mL/min (0.01277 m/min) which, among all tested flow rates, is the closest to the average flow of the groundwater (≈ 0.000003 m/min). The obtained results pointing on possible application of the natural zeolite clinoptilolite as filler in permeable reactive barriers for protection of groundwater from heavy metals pollution.

Glukozinolati su sekundarni metaboliti koji se sintetiziraju iz aminokiselina. Identificirani su u preko 16 biljnih porodica, a najznačajnija je porodica Brassicaceae u koju se ubraja biljka Lepidium sativum L. Glukozinolati su kemijski i biološki neaktivni spojevi te im je zajedničko da su po kemijskoj strukturi β- tioglukozidni-N-hidroksisulfati s varijabilnim bočnim lancem. Kres salata (Lepidium sativum L.) je jednogodišnja kultura koja sadrži mnoge ljekovite tvari, ali je u ljudskoj prehrani slabo rasprostranjena. Navodi se da je kres salata dobar hiperakumulator teških metala. Biljke nemaju potrebu za kadmijem i uglavnom ne podnose koncentracije veće od 1 ppm, no navedena biljka može akumulirati kadmij u tkivima i tolerirati koncentraciju do 100 ppm. U ovom radu opisan je uzgoj biljke Lepidium sativum L. koji je zalijevan s otopinama kadmija različitih koncentracija od 1 do 50 ppm. Razvoj klica praćen je tijekom 7 dana i jedino pri koncentraciji od 50 ppm došlo je do propadanja biljke. Izolacija glukozinolata se vršila ekstrakcijom uz pomoć 70%-tnog metanola uz desulfataciju, dok se analiza vršila vezanom tehnikom UHPLC-DAD-MS/MS. Identificirani su sljedeći glukozinolati: glukotropeolin koji se nalazi u svim uzorcima i 4-metoksiglukobrasicin koji nije pronađen jedino u sjemenu. Glukotropeolin spada u skupinu arilalifatskih, dok 4-metoksiglukobrasicin pripada skupinu heterocikličnih (indolnih) glukozinolata. Sadržaj glukozinolata, s obzirom na to da su se uzorci zalijevali otopinama kadmija različitih koncentracija, nije se značajno mijenjao. U radu je također opisana priprema biljnog materijala za analizu atomskom apsorpcijskom spektroskopijom. Prije početka analiziranja potrebno je napraviti krivulju umjeravanja, zato što se preko nje iščitavaju koncentracije kadmija u biljnom materijalnu. Na temelju dobivenih rezultata izvodi se zaključak da li se biljka Lepidium sativum L. može koristiti kao hiperakumulator kadmija. Glucosinolates are secondary metabolites that are synthesized from amino acids. They were found in over 16 plant families, the most important being the Brassicaceae family, which includes the plant Lepidium sativum L. Glucosinolates are chemically and biologically inactive compounds and have in common that they are chemically β-thioglucoside-N-hydroxysulfates with a variable side chain. The Lepidium sativum L. plant is an annual crop that contains many medicinal substances, but is poorly used in the human diet. Cress salad is known to be a good hyperaccumulator of heavy metals. Plants do not need cadmium and generally do not tolerate concentrations higher than 1 ppm, but this plant can accumulate cadmium in tissues and tolerate concentrations up to 100 ppm. This thesis describes the cultivation of the plant Lepidium sativum L., which was watered with cadmium solutions of different concentrations from 1 to 50 ppm. Sprouts development was monitored for 7 days and only at a concentration of 50 ppm did the plant decay. Isolation of glucosinolate was performed by extraction with 70% methanol with desulfation, while the analysis was performed using UHPLC-DAD- MS/MS. The following glucosinolates were identified: glucotropeolin was found in all samples and 4- methoxyglucobrasicin which was not found only in seeds. Glucotropeolin belongs to the group of arylaliphatic, while 4-methoxyglucobrasicin belongs to the group of heterocyclic (indole) glucosinolates. The glucosinolate content, since the samples were watered with cadmium solutions of different concentrations, did not change significantly. The thesis also describes the preparation of plant material for analysis by atomic absorption spectroscopy. Before starting the analysis, it is necessary to make a calibration curve because the cadmium concentrations in the plant material are read through it. Based on the obtained results, it was concluded that the plant Lepidium sativum L. can be used as a hyperaccumulator of cadmium.

Kadmij je rastlinam nepotreben, vendar zelo dobro dostopen element. Njegova mobilnost in dostopnost rastlinam je večja v tleh s kislo reakcijo. S prenosom v prehranjevalno verigo lahko v prevelikih koncentracijah ogroža zdravje ljudi. Za različne rastlinske vrste je različno dostopen. V letu 2018 so na kmetiji v Šmarjah pri Jelšah, izmerili vsebnost kadmija v radiču, ki je presegala mejno vrednost, čeprav je vsebnost Cd v tleh < 0,5 mg/kg, vendar so tla močno kisla (pH 4,8). Poskus za namen magistrske naloge je bil izveden na isti kmetiji, kjer smo ugotavljali privzem kadmija v 10 užitnih delih 9-ih vrtnin. Poskus je bil izveden v vegetacijskem letu 2019, v treh ponovitvah in je imel dve obravnavanji: kontrolo in apnjeno (uporabljen je bil pripravek Kalcevita za povečanje pH vrednosti tal). Namen magistrskega dela je bil ugotoviti kako apnjenje tal vpliva na privzem kadmija v različne vrtnine. Zanimalo nas je kako se vsebnost kadmija razlikuje v enakih vrtninah na apnjenih in kontrolnih tleh, katera vrtnina je najbolj varna za pridelavo na apnjenih tleh in katere vrtnine se na kmetiji lahko pridelujejo brez apnjenja tal. Spomladi, pred setvijo/sajenjem in jeseni, po rastni dobi vrtnin so bili odvzeti vzorci kontrolnih in apnjenih tal s sondiranjem. Izvedena je bila standarda pedološka analiza tal in analiza celokupne ter dostopne frakcije Cd. Rastlinske vzorce smo odvzeli v tehnološki zrelosti vrtnin. Užitne dele vrtnin smo očistili, posušili in naredili analizo skupne vsebnosti Cd. Ugotovili smo, da je vsebnost kadmija na nekaterih poljinah apnjenih tal večja kot na kontrolnih tleh, nekatere vrtnine so celo presegle normative o mejni vrednosti Cd v živilih. Vsebnost kadmija v povprečju ni bila večja pri vrtninah iz kontrolnih tal. V različnih delih vrtnin se kadmij akumulira v različnem obsegu, kar smo potrdili pri peteršilju. Vsebnost Cd pri korenu peteršilja je na poljini A2 presegla mejno vrednost, v listih pa je bila majhna in se ni približala normativu. Vsebnost kadmija je bila različna pri različnih vrtninah v enakem obravnavanju. Cadmium is not essential for plants growth, but highly available for uptake. Its mobility and availability for plants is higher in acid soil. By being transferred into the food chain, in higher concentrations it can endanger human health. Its availability varies by different plant species. The concentration in chicory elevated on the farm in Šmarje pri Jelšah in 2018. It was confirmed that the limited value was exceeded, although the concentration of Cd in soil was

V magistrski nalogi smo v poljskem poskusu ocenili fitoremediacijski potencial dveh sort navadne konoplje, 'Tisze' in 'Future 75'. Izbrali smo tri poskusne lokacije v Celjski kotlini z različno stopnjo onesnaženosti tal s svincem, cinkom in kadmijem: v kraju Medlog (kontrolna lokacija, neonesnažena s Pb in Zn, malo onesnažena s Cd), v kraju Babno (srednje onesnažena lokacija) in v kraju Bukovžlak (najbolj onesnažena lokacija). Pred setvijo smo na vsaki lokaciji odvzeli združene vzorce tal in določili osnovne pedološke parametre (pH, delež organske snovi in rastlinam dostopna hranila) ter vsebnost Pb, Zn in Cd v tleh. Seme smo z Wintersteigerjevo sejalnico posejali junija 2017, na 18 m2 površine. Poskus smo izvajali v štirih ponovitvah, žetev smo opravili oktobra 2017. Izmerili smo biomaso vsakega rastlinskega dela posebej (korenine, seme, socvetja, ločeno stržen in povrhnjica, pri dvospolni sorti 'Tisza' ločen stržen in povrhnjica tudi po spolu) in privzem kovin v rastlinske dele. Najpogosteje smo največjo koncentracijo Pb, Zn in Cd pri obeh sortah izmerili v socvetjih, sledijo korenine in semena, najmanjši privzem Pb, Zn in Cd je pri obeh sortah v stržen in povrhnjico. V eni rastni dobi fitoremediacija z navadno konopljo še ni učinkovita, v več letih pa bi lahko uspešno očistili malo onesnažena tla. In a master's thesis, in a field experiment, we evaluated the phytoremediation potential of two varieties of hemp (Cannabis sativa L.), 'Tisza' and 'Futura 75'. We selected three experimental locations in the Celje valley with different levels of soil contamination with lead, zinc and cadmium: Medlog was control location, not contaminated with Pb and Zn and slightly contaminated with Cd. In Babno, soil was medium contaminated and in Bukovžlak soil was the most contaminated with Pb, Zn and Cd. Before sowing we took soil samples from each location and determinate the basic pedological parameters (pH, organic matter content, nutrients available to plants) and lead, zinc and cadmium content in the soil. The seeds were sown with the Wintersteiger seeder in June 2017 on an 18 m2 large area. The experiment was performed in four replicates. The harvest was carried out in October 2017. We measured the biomass of each plant part separately (roots, seeds, inflorescences, separately pith and epidermis, in the two genders variety 'Tisza' separately pith and epidermis also by gender) and metal uptake by plant. Most often, the highest concentrations of Pb, Zn and Cd in both varieties were measured in inflorescences, followed by roots and seeds. The lowest uptake of Pb, Zn and Cd is in both varieties the pith and epidermis. In one growing season, phytoremediation with hemp (Cannabis sativa L.) is not effective yet, however, in a few years slightly contaminated soil could be successfully cleared with hemp.

Ispitano je uklanjanje kadmijevih i cinkovih iona na nepomičnom sloju prirodnog zeolita iz vodene otopine (Cd+Zn) koncentracijskog omjera Cd/Zn od 0,13 i 0,14, pri protocima od 1 i 2 mL/min. Prirodni zeolit klinoptilolit pokazao je dobru učinkovitost u uklanjanju Cd i Zn iona iz binarnog sustava pri ispitanim eksperimentalnim uvjetima. Dobiveni rezultati uspoređeni su s binarnim sustavom (Pb+Zn) za iste eksperimentalne uvjete. Utvrđen je efekt istiskivanja iona Zn iz strukture zeolita ionima Cd i Pb iz početne otopine. Zn je prekoračio svoju početnu koncentraciju za 1,2 puta u prisutnosti Cd te čak 2,3 puta u prisutnosti Pb. Efekt istiskivanja u sustavu (Pb+Zn) može se pripisati puno manjem hidratiziranom radijusu iona Pb u odnosu na ion Zn, a time i njegovu većem afinitetu. Istiskivanje u sustavu (Cd+Zn) bilo je iznenađujuće zbog vrlo sličnih fizikalno-kemijskih svojstava tih dvaju iona. Pri Cd/Zn = 0,14 te Pb/Zn = 0,19 i protoku od 1 mL/min u oba sustava utvrđeno je bolje vezanje iona Zn u odnosu na ione Cd i Pb, unatoč njegovu slabijem afinitetu. Tor ukazuje da je moguće preferencijalno vezanje iona Cd i Pb kontrolirati početnom koncentracijom iona Zn u binarnom sustavu. Ukupni koeficijent prijenosa tvari veći je za (Cd+Zn) nego za (Pb+Zn) sustav zbog manje izražene kompeticije i migracije iona, a time i manjeg otpora. Najsporiji stupanj je difuzija kroz film te ona kontrolira ukupnu brzinu procesa. The removal of cadmium and zinc ions onto fixed zeolite bed from (Cd+Zn) aqueous solution for the Cd/Zn concentration ratios of 0.13 and 0.14, and for the flow rates of 1 and 2 mL/min has been investigated. The natural zeolite clinoptilolite showed good efficiency in Cd and Zn removal from binary system, for examined experimental conditions. The obtained results have been compared with the (Pb+Zn) binary system for the same experimental conditions. The displacement of Zn ions from the zeolite structure by the Cd and Pb ions from the initial solution has been determined. The Zn exceeded its initial concentration up to 1.2 times in the presence of Cd, and up to 2.3 times in the presence of Pb. The displacement effect in the (Pb+Zn) system can be attributed to the much smaller hydrated radius of Pb ion, compared to the Zn ion, and thus to its higher affinity. The displacement in the (Cd+Zn) system was quite surprising due to very similar physicochemical properties of these two ions. In both systems, for Cd/Zn = 0.14 and Pb/Zn = 0.19 for flow rate of 1 mL/min, the better binding of Zn compared to Cd and Pb has been obtained despite its lower affinity. This is of great importance because it indicates that it's possible to control preferencial binding of Cd and Pb ions by the initial Zn ion concentration in binary systems. The overall mass transfer coefficient shows higher values for the (Cd+Zn) system compared to the (Pb+Zn) system, due to the reduced competition, ions migration and thus the lower resistance. The diffusion through the film is the slowest step responsible for the overall process rate.

V diplomski nalogi smo proučevali, kako se navadna konoplja odziva na zelo visoke koncentracije kadmija, svinca in cinka v tleh in kakšen je učinek posameznega elementa na rast in razvoj rastline. V lončnem poskusu smo testirali sprejem posamezne težke kovine: kadmija (Cd), svinca (Pb) in cinka (Zn) v različne dele dveh sort ('Tisza' in 'Futura 75') navadne konoplje. Iz neonesnaženih tal smo z dodajanjem težkih kovin v kloridnih oblikah (PbCl2, CdCl2H20, ZnCl2) pripravili dve stopnji kontaminacije tal za vsak posamezen element: Pb-1/2 (1000 mg/kg), Pb-2/2 (1500 mg/kg ), Cd-1/2 (50 mg/kg), Cd-2/2 (100 mg/kg), Zn-1/2 (2500 mg/kg) in Zn-2/2 (5000 mg/kg). Rastline smo gojili tudi v nadzorovanih neonesnaženih tleh. Rastline smo gojili v loncih volumna 3,5 L do botanične zrelosti. V vsakem loncu je bila posajena ena rastlina, za eno obravnavanje smo uporabili 10 loncev iste sorte,10 rastlin sorte 'Tisza' in 10 rastlin sorte 'Futura 75. Poskus je potekal v rastlinjaku med januarjem in julijem 2018. Žetev je potekala julija 2018, ko je bilo seme zrelo. Za določanje težkih kovin v različnih rastlinski delih smo vzorčili: korenine (ločeno za glavne in stranske), steblo (ločeno za stržen in povrhnjico) in socvetja. Največ Cd, Pb in Zn so rastline obeh sort privzele v stranske korenine, fitotoksične učinke je bilo opaziti samo, kjer smo v tla dodali ZnCl2, tam so rastline propadle zaradi prevelike koncentracije soli. Vsi rastlinski deli konoplje, ki je rastla v tleh onesnaženih s težkimi kovinami, vsebujejo težke kovine, zato je njihova uporaba omejena. In the thesis, we studied how hemp responds to extremely high concentrations of cadmium, lead and zinc in the soil and the effects of each given element on the growth and development of the plant. In a pot experiment, we tested the uptake of heavy metals: cadmium (Cd), lead (Pb), and zinc (Zn) into various parts of two hemp varieties ‘Tisza’ and ‘Futura 75’. For each element, two levels of soil contamination were prepared by adding heavy metals in chloride forms to non-contaminated soil: Pb-1/2 (1000 mg/kg), Pb-2/2 (1500 mg/kg), Cd-1/2 (50 mg/kg), Cd-2/2 (100 mg/kg), Zn-1/2 (2500 mg/kg) in Zn-2/2 (5000 mg/kg). The plants were grown in 3,5 L pots, one plant per pot, 10 plants of each variety in each combination, 70 plants together with control soil. The experiment was carried out in a greenhouse between January and July 2018. The results were harvested in July 2018 when the seeds were ripe. To determine the presence of heavy metals in various parts of the plant, we sampled: roots (primary and lateral individually), the stem (fibres and hurds individually), and inflorescences. Both of the varieties showed the highest content of Cd, Pb, and Zn in the fibrous roots, while phytotoxic effects (the plants decayed) were observed only in combinations where ZnCl2 was added and it was a concesuence of a high salt concentration. All parts of hemp grown in the soil contaminated with heavy metals contain heavy metals, therefore their use is limited.

Murina (Muraena helena L.) mediteranska je vrsta ribe poznata iz antičkih vremena, zanimljiva sa biološkog, i komercijalnog stajališta. Zbog bentičkog i višegodišnjeg načina života, sedentarnog stila života, ograničene stope migracije zajedno s brzinom rasta i konzumiranjem širokog raspona vrsta na različitim trofičkim pozicijama, ova vrsta mogla bi biti zanimljiv potencijalni bioindikatorski organizam za proučavanje bentičkog zagađenja teškim metalima u Jadranu/Mediteranu. Ovim se radom nastoji pokazati kako se glavni rezidualni metali akumuliraju unutar različitih organa ove vrste. Murine su prikupljene u nezagađenom području Jadranskog mora, Elafiti-Dubrovnik u ljetnom i zimskom periodu. Cilj rada je pokazati bioakumulacijski potencijal različitih organa za metale Hg, As, Cd, Pb i odrediti koji organi bi bili najbolji za bioindikatorski potencijal nakupljanja metala iz morskog okoliša. U većini organa, osim srca, najveća je bioakumulacija tijekom ljetnog perioda. Iznimno u zimskom periodu, živa i arsen akumuliraju se najviše samo u mišićnom tkivu. Od svih istraživanih metala, promatramo li sve prikupljene uzorke riba bez obzira na sezonu, živa je najzastupljeniji akumulirani metal u svim organima osim srca i kože. Koža najviše nakuplja olovo. Arsen je drugi po zastupljenosti metal prisutan u većini organa osim jetre i škrga (u škrgama je olovo jednako zastupljeno po postotnom udjelu). Iako je olovo treće po zastupljenosti u svim organima (osim škrga), postotni udio koncentracije u odnosu na druge metale nije zanemariv i relativno je visok. Najveće dosegnute prosječne koncentracije za živu su oko 0,5 mg/kg u jetri i oko 0,25 mg/kg u kostima, za arsen oko 0,2 mg/kg u škrgama, za olovo oko 0,175 mg/kg u kostima a za kadmij 0,25 mg/kg u koži. Moray eel (Muraena helena L.) is a Mediterranean species of fish known from ancient times, interesting from a biological and commercial point of view, and due to its benthic and perennial lifestyle, sedentary lifestyle, limited migration rate along with growth rate and consumption of a wide range of species in different trophic positions, this species could be an interesting potential bioindicator for studying benthic heavy metal pollution in the Adriatic / Mediterranean. This paper shows how the major residual metals accumulate within different organs of this species. Moray eels were collected in the unpolluted area of the Adriatic Sea, Elafiti-Dubrovnik in summer and winter period. The aim of the work is to show the bioaccumulation potential of different organs for metals Hg, As, Cd, Pb and to determine which would be best for the bioindicative potential for the accumulation of metals from the marine environment. In most organs, except the heart, the highest bioaccumulation occurs during the summer. Exceptionally, in winter, mercury and arsenic accumulate most only in muscle tissue. Of all the metals studied, if we look at all collected samples regardless of season, mercury is the most represented accumulated metal in all organs except heart and skin. The skin mostly accumulates lead. Arsenic is the second most abundant metal present in most organs except liver and gills (in gills lead is equally abundant by percentage). Although lead is the third largest in all organs (except gills), the percentage concentration relative to other metals is not negligible and is relatively high. The highest average concentrations reached for mercury are about 0.5 mg/kg in the liver and about 0.25 mg/kg in the bones, for arsenic about 0.2 mg/kg in the gills, for lead about 0.175 mg/kg in the bones and for cadmium 0.25 mg/kg in the skin.

U ovom je radu ispitivan utjecaj pH tla i dodatka kompleksirajućeg agensa na sadržaj kadmija u pojedinim biljkama. Tlo upotrijebljeno za ovaj eksperiment uzeto je s površina uz prometnicu u neposrednoj blizini Željezare u Zenici. Kompleksiranje tla izvršeno je s otopinom dinatrijeve soli etilendiaminotetraoctene kiseline, Na2H2Y, a snižavanje pH tla otopinom aluminijeva sulfata, Al2(SO4)3. Za navedena ispitivanja upotrijebljene su sljedeće biljke: zelena salata (Lactuca sativa var. capitata), mješavina trava, djetelina (Trifolium repens), kukuruz (Zea mays) i kopriva (Urtica dioica). Određivanje sadržaja kadmija u pripremljenom tlu i biljkama provodilo se spektrometrijskom metodom ICP-OES atomskim emisijskim spektrometrom, Perkin Elmer 7000DV. Rezultati provedenih ispitivanja pokazuju da smanjenje pH tla i kompleksiranje tla (kiselog i alkalnog) dovodi do povećanja akumulacije kadmija iz tla u nadzemne dijelove ispitivanih biljaka.

Niska koncentracija cinka u tlima rezultira niskom koncentracijom toga elementa i u prehraniljudi i životnja. Kako je cink esencijalan element, njegov deficit nepovoljno utječe na organizam. S druge strane, kadmij je toksičan element bez esencijalnog i korisnog učinka, te je stoga poželjno da ga u konzumnim namirnicama bude što manje. Agronomska biofortifikacija rezultira povećanjem cinka u jestivim dijelovma biljaka,a time i većim količinama unosa cinka u ljudski organizam. Cilj ovoga istraživanja bio je utvrditi utjecaj folijarne aplikacije cinka na koncentraciju cinka i kadmija u biljnim dijelovima (osobito zrnu) pojedinih sorata soje. Biofortifikacijski pokus proveden je 2017. godine na 6 sorata soje (Korana, Sanda, Lucija, Toma, Sunce, Ika) različitih grupa zriobe (00I). Folijarna aplikacija cinka u obliku cink sulfata (5,489 kg/haZnSeO4×H2O) provedena je u fenofazi cvatnje soje. Biofortifikacija soje je značajno utjecala na koncentracije cinka u mahunama, stabljici i zrnu (povećanje 106%, 48,5%, odnosno 25%) te iznošenje cinka prinosom zrna (povećanje 34,75%). Tretman nije statistički značajno utjecao na koncentraciju kadmija u stabljici, mahunama i zrnu soje te njegovo iznošenje prinosom zrna, ali je utvrđeno malo smanjenje koncentracija u stabljici (23%), mahunama (31%) i zrnu (22,64%). Utvrđen je i statistički značajan utjecaj sorata na prinos te akumulaciju kadmija u biljnim dijelovima i njegovo iznošenje zrnom soje. Utjecaj sorata na koncentraciju cinka i njegovo iznošenje zrnom soje nije bilo statistički značajno. Rezultati navode na zaključak da se folijarnom aplikacijom cinka povećava njegova koncentracija u zrnu, mahunama i stabljici soje. Sorte soje ne razlikuju značajno po akumulaciji i iznošenju apliciranog cinka, ali se razlikuju po akumulaciji i iznošenju kadmija prinosom. Utvrđeni rezultati značajnog povećanja koncentracija Zn u zrnu soje agronomskom biofortifikacijom i istovremeno značajnih razlika između sorata soje u prinosu i koncentracijama kadmija u zrnu, ukazuju da se pažljivim izborom sorte i biofortifikacijom može proizvesti zrno soje visokih koncentracija cinka, istovremeno niskih kocentracija kadmija te dostatno visokih prinosa., Low Zn concentrations in soils result with low concentrations of this element in human and animal nutrition. Since zinc is an essential element, his deficit has an adversely affects at the organism. On the other side, cadmium is a toxic element without any essential and useful effect, and because of that is better that be as little as possible in consumed foodstuffs. Agronomic biofortification results with increasing Zn concentrations in edible parts of plants, and increasing intake of this element into the human organism. The aim of this experiment was been to determine the influence foliar application of zinc on the concentration of zinc and cadmium in plant parts (especially grain) some soybean types. Biofortification experiment was carried out in 2017 on 6 soya cultivars (Korana, Sanda, Lucija, Tom, Sun, Ika) with different lenght of vegecation (00-I). The foliar application of zinc, like zinc sulphate (5.489 kg ha1ZnSeO4 × H2O), was applied in flowering phenophase of soybean. Biofortification of soya was a statistically significant effected on the amount of zinc in pods, stems and grain (increase 106%, 48.5% and 25%) and his taken out with grain yield (34.75%). The treatment didn't statistically significantly affected on the amount of cadmium in stems,pods and soybean grain, and his taken out with grain yield, but there was a decrease; 23% in stems, 31% in pods and 22.64% in grain. Cultivars significantly affected on yield, accumulation of Cd in parts of plant, and his removal with soy bean. The influence of cultivars on zinc concentration and his taken out with yield wasn't been statistically significantly. The results suggest that foliar zinc application increases his concentration in grain, pods and stems of soya. Soya varieties are not significantly different in accumulation and taking out of the applied zinc, but are different in accumulation and taking out of cadmium with yield. The results of a significant increase Zn concentration in soybean grain by agronomic biofortification and at the same time significant differences between soya varieties in yield and concentrations of cadmium in the grain indicate that with careful selection of varieties and biofortification we can produce soya grain with high zinc,and at the same time low cadmium concentration, and sufficiently high yields .

U ovom radu ispitan je utjecaj saliniteta i kadmija na brzinu rasta, fiziološki odgovor, oblik stanica i adhezijsko ponašanja na elektrodi, fitoplanktonske morske vrste Dunaliella tertiolecta Butcher. Korištene su mikroskopske i elektrokemijske metode polarografije i kronoamperometrije na kapajućoj živinoj elektrodi. D. tertiolecta nema čvrstu, celuloznu staničnu stijenku za razliku od ostalih zelenih algi, što je čini osjetljivom na promjene u ekosustavu i zbog čega je često korišten modelni organizam u istraživanjima stresa. Prilagodba stanica D. tertiolecta u uvjetima nižeg saliniteta u kulturi ukazuje na nešto veću dimenziju stanice, promjenu u sferični oblik stanice, te nešto brži rast, dok je adhezijsko svojstvo prianjanja u širokom području potencijala ostalo sačuvano. Prilagodba stanica na prisustvo teškog metala kadmija u kulturi rezultirala je smanjenjem gustoće stanica, smanjenjem dimenzije, promijenom oblika, pojavom površinski-aktivnih čestica i mikroagregata u mediju, što ukazuje na promijenjene metaboličke aktivnosti stanica uslijed stresa. Rezultati ovog rada doprinose boljem razumijevanju adhezijskog ponašanja stanica fitoplanktona u stresnim uvjetima in vitro, te unaprijeđuju znanje o preživljavanju i prilagodbi fitoplanktonskih organizama na prirodnim međupovršinama u vodenom okolišu u uvjetima opterećenja. In this Thesis is examined the influence of salinity and presence of heavy metal cadmium in culture on the response of marine phytoplankton Dunaliella tertiolecta Butcher in terms of growth rate, physiological activity, cell shape and adhesion behavior on the electrode. Microscopic and electrochemical methods of polarography and chromoamperometry at the dropping mercury electrode were used. D.tertiolecta cell has no solid cellular cell wall in contrast to other green algae, which makes it susceptible to changes in the ecosystem and is why a model organism is often used in stress research. Adaptation of D. tertiolecta cell culture in lower salinity conditions suggests a slightly larger cell dimension, a change in spherical cell shape, a somewhat faster growth, while the adhesion properties at the broader potentials area remains preserved. Adaptation of phytoplankton to the presence of heavy metal cadmium in culture resulted in decrease of cell density with increasing cadmium concentration, cells are slightly smaller in size and show a deterioration in shape, the occurrence of surface active particles and microagregates in the culture which could be the result of the changed metabolic activity of cells due to stress. These results contribute to a better understanding of the adhesion behavior of phytoplankton cells in stress conditions in vitro and improve knowledge about survival and adaptation of phytoplankton organisms at natural interfaces in the aquatic environment under pressure.