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Namen raziskave je bil ugotoviti mineralno in geokemično sestavo vzorcev sedimenta Koseškega bajerja, ki se nahaja na severozahodnem delu Ljubljanske kotline. Iz sredine jezera smo odvzeli jedro vrtine KS in naredili natančen sedimentološki popis jedra, granulometrijsko analizo vzorcev ter pripravili vzorce za nadaljnje raziskave. Ugotovili smo, da naši vzorci pripadajo trem skupinam: malo peščen meljast pesek, zelo malo meljasta peščena glina in malo meljast glinen pesek. Z rentgensko praškovno difrakcijo (XRD) smo v obravnavanih vzorcih določili kremen, dolomit, albit, sadro, illit in kalcit. V izbranih vzorcih KS-20, KS-40, KS-55 in KS-65 smo našli glinene minerale illit, klorit in kaolinit. Z visoko ločljivostnim masnim spektrometrom z induktivno sklopljeno plazmo (HR-ICP-MS) smo v vzorcih določili detajlno elementno sestavo glavnih oksidov in težkih kovin. V vzorčni vrtini smo našli največjo vsebnost SiO2 (43,31–74,76 %), kateri sledi Al2O3 (12,52–17,25 %), najmanj pa je MnO (0,02–0,07 %). Najvišje vsebnosti težkih kovin, pripadajo elementom Cu (273,6 mg/kg), Zn (266 mg/kg), Pb (106,8 mg/kg) in Cd (2,2 mg/kg), najnižje vsebnosti pa elementom Sb (0,6 mg/kg), As (14,6 mg/kg), Mo (4,7 mg/kg) in Ni 36(mg/kg). Z statističnimi analizami smo dokazali, da se vsebnosti težkih kovin z globino znižujejo, posledično lahko sklepamo, da so v zgornjih cm jedra zvišane vsebnosti težkih kovin antropogenega izvora. Gre predvsem za vpliv kmetijstva, prometa in kurjave. Mineraloško in elementno sestavo vzorcev smo potrdili tudi z uporabo elektronske mikroskopije, in sicer z vrstičnim elektronskim mikroskopom s spektrometrom energijske disperzije (SEM-EDS). Potrdili smo naslednje minerale: kremen, kalcit, sadro in glinene minerale. V omenjenih vzorcih pa smo zaznali minerale, ki lahko veljajo kot potencialni nosilci težkih kovin: cirkon, ilmenit, rutil, pirit in minerali REE. The aim of the study was the mineralogical and geochemical analysis of the sediments of the Koseze Lake, located in the northwestern part of Ljubljana. We took the core from the KS well in the middle of the lake. The core was then taken to the Department of Geology at the Faculty of Natural Sciences, where we conducted a detailed sedimentological inventory of the core and granulometric analysis of the samples. We determined that our samples belonged to three groups: slightly sandy-silty sand, very slightly silty-sandy clay, and slightly silty-clay sand. X-ray powder diffraction (XRD) was used to determine quartz, dolomite, albite, chlorite, kaolinite, gypsum, illite, and calcite in the samples studied. The clay minerals illite, chlorite and kaolinite were found in selected samples KS-20, KS-40, KS-55 and KS-65. Using a high-resolution inductively coupled plasma mass spectrometer (HR-ICP-MS), we determined the detailed elemental composition of the major oxides and heavy metals in the samples. HR-ICPMS Analysis of the oxides revealed the highest SiO2 content (43.31-74.76%), followed by Al2O3 (12.52-17.25%) and the lowest MnO (0.02-0.07%). The highest heavy metal contents show the elements Cu (273,6 mg/kg), Zn (266 mg/kg), Pb (106 mg/kg) and Cd (2,2 mg/kg). The statistical analyses have shown that the heavy metal contents decrease with depth, from which we conclude that the increased heavy metal contents are of anthropogenic origin. This is mainly due to the impact of agriculture, transport and heating. The mineralogical and elemental composition of the samples was also confirmed by electron microscopy using a scanning electron microscope with energy dispersion spectrometer (SEM-EDS). The minerals confirmed with SEM-EDS were quartz, calcite, gypsum and clay minerals. In the samples mentioned above, we also detected minerals that are potential carriers of heavy metals: zircon, ilmenite, rutile, pyrite and REE minerals.

Tobak (Nicotiana tabacum) je eden izmed vodilnih produktov potrošniške družbe. Njegova uporaba predstavlja grožnjo javnemu zdravju, saj lahko tobak zaradi kopičenja potencialno nevarnih kovin (PNK) poleg katrana, ogljikovega monoksida in nikotina škodljivo vpliva na človeško telo. Namen diplomskega dela je na osnovi znanstvenih virov predstaviti najpogostejše vire PNK v tobaku, vsebnosti kovin v tleh, kjer pridelujejo tobak, mehanizme privzema PNK iz tal v tobak ter dejavnike vpliva, kot so talne lastnosti, sorte tobaka in kmetijske prakse. Skozi pregledane raziskave je bilo ugotovljeno, da je najpogostejši vir PNK v tobaku uporaba fosfatnih gnojil. Mehanizmi kopičenja kovin v tobaku omogočajo prenos PNK iz tal v korenine, nato v nižje ležeče liste, čemur sledi prehajanje v višje rastoče liste tobaka. Prisotnost PNK v tleh se razlikuje glede na onesnaženost območij, kjer gojijo tobak. Največ PNK se nahaja v tobaku, ki ga gnojijo z gnojili z večjo vsebnostjo PNK. Nanašanje fitofarmacevtskih sredstev (FFS) preko tal povzroči manjše vsebnosti PNK v tobaku v primerjavi s pršenjem na vršičke tobaka. Sorta tobaka prav tako lahko vpliva na sprejem PNK v rastlino. Vendar v nobeni raziskavi ni bila ugotovljena problematična vsebnost kovin v tobaku. Tobacco (Nicotiana tabacum) is one of the leading articles of human consumption. Its use represents a threat to public health, due to its ability to accumulate potentially hazardous metals (PHM) as well as tar, carbon monoxide and nicotine, which can have a harmful effect on the human body. The purpose of the bachelor’s thesis was to review of previous publications on the most common sources of PHM in tobacco, the content of metals in soils where tobacco is grown, the mechanism of PHM uptake from soil into tobacco, and the influencing factors (soil properties, type of tobacco, agricultural practices). Review of research results showed that the most common source of PHM in tobacco is the use of phosphate fertilizers. The mechanisms of PHM accumulation in tobacco allow the transfer of PHM from soils to the lower leaves, and then the PHM transfers to the higher growing tobacco leaves. The presence of PHM in soil varies depending on the contamination of the tobacco growing areas. More PHM is found in tobacco fertilized with a higher PHM content in fertilizers. The application of plant protection products (PPPs) on the soil results in lower PHM values in tobacco compared to spraying of tobacco tops. Tobacco variety also affects PHM uptake into the plant. Several studies were conducted, however none of them detected problematic metal content in tobacco.

V naprej določenemu koncentracijskemu gradientu treh težkih kovin (svinec, cink, kadmij) sem dodajal ligande (EDTA, citronska kislina in huminska kislina). Z meritvami na osnovi atomske absorpcijske spektroskopije (AAS) sem za vsako kombinacijo določil umeritveno krivuljo in njen naklon. S primerjavo naklonov sem določal vpliv dodanega liganda na določanje posamezne kovine oz. njihovi zmesi v različnih medijih (nevtralnem in kislem) na metodo za določanje teh kovin. Svinec se je izkazal za najbolj robustnega na spreminjajoče se dejavnike, medtem ko je bil kadmij najbolj podvržen spremembam naklona zaradi spreminjajočih se dejavnikov. I added ligands (EDTA, citric acid, and humic acid) in a predetermined gradient of 3 heavy metals (lead, zinc, and cadmium). The calibration curve and slope for each combination were determined using atomic absorption spectroscopy (AAS) measurements. By comparing the slopes, I studied the influence of the added ligand to the individual element solution or their mixtures in different media (neutral and acidic) on the method for determining the concentration. Lead was found to be the most resistant to factor changes, whereas cadmium was most prone to slope changes because of factor changes.

V okviru diplomskega dela smo določali koncentracije izbranih težkih kovin v površinski vodi reke Kamniške Bistrice z namenom identifikacije tveganja, ki ga predstavljajo za zdravje. Na podlagi podatkov, ki jih navaja ARSO v vsakoletnih meritvah kakovosti vode, smo izbrali kovine aluminij (Al), antimon (Sb), arzen (As), baker (Cu), cink (Zn), kobalt (Co), krom (Cr), molibden (Mo), nikelj (Ni) in svinec (Pb). Terensko delo smo izvedli v maju 2022, kjer smo odvzeli vzorce na štirih zajemališčih ob vodotoku. Vzorce smo prefiltrirali in redčili z 1 % HNO3. Za natančno določevanje koncentracij smo uporabili standardno analitsko multi-elementarno tehniko induktivno sklopljeno plazemsko atomsko emisijsko spektroskopijo (ICP-OES). Za pripravo standardnih raztopin smo uporabili Merck (VI) KGaA. Dobljene rezultate smo primerjali z zakonsko določenimi mejnimi vrednostmi slovenske in tuje zakonodaje, prav tako pa sem jih primerjal z letnimi meritvami Agencije RS za okolje. Meritve so pokazale povečane koncentracije Al, As, Cu, Zn in Ni v primerjavi z vsakoletnimi meritvami ARSO. Koncentracije elementov Sb, Co, Cr, Mo in Pb so pod mejo detekcije izbrane metode. Mejne vrednosti kljub povišanim koncentracijam za večino elementov niso bile prekoračene, z izjemo Al. Aluminij presega zakonsko določeno mejno vrednost na merilnih mestih v bližini Ihana in iztoka v Savo pri Beričevem. Na merilnem mestu pri Volčjem Potoku se tej meji močno približa. Za aluminij smo pripravili tudi oceno tveganja, v kateri podajamo oceno B in predlagamo nadaljnje spremljanje stanja s povečano frekvenco in poročanje o morebitnih spremembah. Vremenski pogoji, ki so vključevali padavine pred dnevom vzorčenja in gradbena dela v bližini izvira, lahko vplivajo na dejanske rezultate zaradi kontaminacije, povišanega vodnega nivoja in motnosti. As part of the bachelor’s degree, we determined the concentrations of selected heavy metals in the surface water of the Kamniška Bistrica River to identify the risks they pose to health. We chose aluminium (Al), antimony (Sb), arsenic (As), copper (Cu), zinc (Zn), cobalt (Co), chromium (Cr), molybdenum (Mo), nickel (Ni), and lead (Pb) based on data provided by ARSO in their annual water quality measurements. We carried out fieldwork in May 2022, where we collected samples at four points along the watercourse. The samples were filtered and diluted with a 1 % HNO3 solution. We used the standard analytical multi-element inductive coupled plasma atomic emission spectroscopy (ICP-OES) to determine the precise concentrations. A multi-standard solution from Merck (VI) KGaA was used to prepare the standard solutions. We compared the obtained results to the legally defined limit values of Slovenian and foreign legislation, furthermore, we compared them to the annual measurements of the Environmental Agency of the Republic of Slovenia. Measurements showed increased concentrations of Al, As, Cu, Zn, and Ni compared to the annual ARSO measurements. We were not able to determine the exact concentrations of the elements Sb, Co, Cr, Mo, and Pb, as they were below the detection limit. Limit values were not exceeded for most elements in spite of elevated concentrations, Al being the exception. Aluminium exceeds the legally set limit value at the measuring points near Ihan and at the outflow into the river Sava near Beričevo. Values almost reach the limit value at the measuring point near Volčji Potok. We have also prepared a risk assessment for aluminium, giving it a B rating and suggesting further monitoring of the situation with increased frequency and reporting of any changes. Weather conditions that included precipitation before the day of sampling and construction work near the water source may affect actual results due to contamination, elevated water levels, and turbidity.

Soil chemistry of toxic metalloids and metals differs, making their simultaneous removal difficult. Soil contaminated with As, Pb, Zn and Cd was washed with oxalic acid, Na-dithionite and EDTA solution. Toxic elements were removed from the washing solution by alkalinisation with CaO to a pH 12.5: As was co-precipitated with Fe from Fe-EDTA chelate formed after the soil washing. The toxic metals precipitated after substitution of their EDTA chelates with Ca. The novel method was scaled up on the ReSoil® platform. On average, 60, 76, 29, and 53% of As, Pb, Zn, and Cd were removed, no wastewater was generated and EDTA was recycled. Addition of zero-valent iron reduced the toxic elements’ leachability. Remediation was most effective for As: phytoaccessibility (CaCl$_2$ extraction), mobility (NH$_4$NO$_3$), and accessibility from human gastric and gastrointestinal phases were reduced 22, 104, 6, and 51 times, respectively. Remediation increased pH but had no effect on soil functioning assessed by fluorescein diacetate hydrolysis, dehydrogenase, β-glucosidase, urease, acid and alkaline phosphatase activities. Brassica napus produced 1.9 times more biomass on remediated soil, accumulated no As and 5.0, 2.6, and 9.0 times less Pb, Zn and Cd, respectively. We demonstrated the novel remediation technology as cost-efficient (material cost = 41.86 € t$^{−1}$) and sustainable.

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.

Raziskave že desetletja uvrščajo navadno konopljo (Cannabis sativa L.) med hitro rastoče, nezahtevne, hiperakumulativne rastline. Pripisujejo ji visoko stopnjo privzema težkih kovin, medtem ko geni, odzivni na prisotnost potencialno toksičnih kovin, pri navadni konoplji še niso sekvencirani in anotirani, s tem pa tudi ni dodobra raziskana njihova potencialna vključenost v privzem kovin. Ta raziskava skuša zapolniti vrzel nasprotujočih si ali nepopolnih podatkov v literaturi in preučuje vključenost genov GSR 1, PLD α, PDR 12 in HMA 4 v metabolizmu potencialno toksičnih kovin v navadni konoplji. Raziskava temelji na lastnih eksperimentalnih podatkih ter analizah v kontroliranem lončnem poskusu, pri čemer smo preučevali vključenost genov na dve potencialno toksični kovini, svinec in kadmij, pri dveh sortah navadne konoplje, Futura 75 in Tisza. Z načrtovanjem začetnih oligonukleotidov na podlagi medvrstno ohranjenih genskih zaporedij - ortologov v že anotiranih vrstah, kot so Arabidopsis thalinana, Brassica juncea, Lactuca sativa, Triticum urartu ter Vitis vinifera, pa raziskava nudi tudi posredni vpogled v podobnost nukleotidnih zaporedij tovrstnih genov v navadni konoplji. Research has classified industrial hemp (Cannabis sativa L.) as a fast-growing, undemanding, hyperaccumulative plant for decades. It is also attributed a high level of heavy metal uptake, while genes responsive to the presence of potentially toxic metals in industrial hemp have not been sequenced and annotated, and their involvement in their uptake is not well understood. The study tries to fill the gap of conflicting or incomplete data in literature, and investigates the involvemenet of GSR 1, PLD α, HSP70, PDR 12, and HMA 4 genes in the response of industrial hemp to potentially toxic metals. The study is based on our own experimental data and analyses in a controlled pot experiment, whereby we evaluated the involvement of genes in the response to two potentially toxic metals, lead and cadmium, in two separate varieties of hemp, Futura 75 and Tisza. By designing the initial oligonucleotides on the basis of interspecific preserved gene sequences - orthologs in already annotated species such as Arabidopsis thalinana, Brassica juncea, Lactuca sativa, Triticum urartu and Vitis vinifera, the study also offers an indirect insight into the similarity of nucleotide sequences of these genes in industrial hemp.

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.

Heavy metal abundance and potential environmental risks are reported for surface sediments (n = 21) from the Port of Koper area, Republic of Slovenia. The enrichment factor (EF) indicates minor enrichment in arsenic (As), cadmium (Cd), copper (Cu), molybdenum (Mo), lead (Pb), antimony (Sb), and zinc (Zn), moderately to severely enriched with nickel (Ni). The trace metal chemistries, in the context of sediment quality guidelines (SQG), imply adverse threshold effect concentrations (TEC) and probable effect concentrations (PEC), for Ni only. Sediment sequential leaching experiments demonstrated that the majority of heavy metals were of natural lithogenic origin and low bioavailability. The heavy metals’ potential for “Risk Assessment Code” values exhibited no or low anthropogenic environmental burden, with the exception of Mo.

V diplomskem delu smo raziskovali onesnaženost sedimenta potoka Drtijščica s težkimi kovinami, tako da smo ustrezno pripravljene vzorce sedimenta analizirali z analitsko tehniko induktivno sklopljeno plazmo atomsko emisijsko spektroskopijo (ICP-OES). Omenjena analitska tehnika omogoča hkratno določanje več elementov v vzorcu z izjemno natančnostjo. Analizirali smo sledeče težke kovine: arzen (As), baker (Cu), cink (Zn), kadmij (Cd), kobalt (Co), krom (Cr), molibden (Mo), nikelj (Ni) in svinec (Pb). Izmerili smo tudi pH in temperaturo vode nad sedimentom. V okviru terenskega dela smo vzorce sedimenta odvzeli na šestih odvzemnih mestih, in sicer prvič februarja leta 2020 in drugič marca leta 2021. Pred analizo vzorcev na aparaturi ICP-OES smo aparaturo umerili z multistandardno raztopino Merck VI (MS6) ter pridobili umeritvene premice posameznih težkih kovin. Umeritvene premice predstavljajo odvisnost znane koncentracije znanega elementa od intenzitete, ki je določena s standardom. Pri laboratorijskem delu smo uporabljali ustrezno zaščitno opremo – haljo, rokavice, zaščitna očala in zaradi preprečevanja širjenja virusa sars-cov-2 tudi zaščitno masko za obraz. Ugotovili smo, da je bila povprečna pH-vrednost prvega vzorčenja blizu nevtralne vrednosti, povprečna vrednost drugega vzorčenja pa se je pomaknila v bazično področje. Presežene mejne vrednosti za As in Cd smo ugotovili na dveh odvzemnih mestih. Vrednosti preostalih preiskovanih težkih kovin niso presegle mejnih vrednosti. Prisotnost povišanih koncentracij težkih kovin v sedimentu služi kot dokaz obstoja antropogenega vpliva na vodni ekosistem ter z njim povezana tveganja za varnost in zdravje ljudi. In my bachelor’s degree thesis I studied heavy metal contamination of sediment in the local stream Drtijščica. For evaluation of content of heavy metals, the samples were appropriately prepared and analysed with inductively coupled plasma atomic emission spectroscopy (ICP-OES). This analytic technique enables simultaneous evaluation of multiple elements in the sample with high precision. The following heavy metals were analysed: As, Cu, Zn, Cd, Co, Cr, Mo, Ni, Pb. Additionally, sediment pH value and temperature were measured at the time of sampling. Six sampling points were chosen. Samples were collected two times. First ones were collected in February 2020 and second ones in March 2021. ICP-OES machine was calibrated using multi standard solution Merck VI (MS6) before the analysis. During laboratory work personal protective equipment was used. The results from the analysis showed elevated average pH value of the second sampling. Limit values of As and Cd were exceeded on two sampling points. Limit values of all other heavy metals were not exceeded. The presence of elevated concentrations of heavy metals serves as an indicator of anthropogenic influence on the stream ecosystem and the risks it brings for human health and safety.

In this study, we evaluated the impact of washing of Pb, Zn and Cd contaminated soil using EDTA-based technology (ReSoil®) on soil biological properties by measuring some of the most commonly used/sensitive biological indicators of soil perturbation. We estimated the temporal dynamics of the soil respiration, the activities of soil enzymes (dehydrogenase, β-glucosidase, urease, acid and alkaline phosphatase), and the effect of the remediation process on arbuscular mycorrhizal (AM) fungi in original (Orig), remediated (Rem) and remediated vitalized (Rem+V) soils during a more than one-year garden experiment. ReSoil® technology initially affected the activity level of soil microbial respiration and all enzyme activities except urease and reduced AM fungal potential in the soil. However, after one year of vegetable cultivation and standard gardening practices, soil microbial respiration, acid and alkaline phosphatase in the Rem and Rem+V reached similar activities as in the Orig. Only the activities of dehydrogenase and β-glucosidase remained lower in the remediated soil compared to the Orig. The frequency of arbuscular mycorrhiza in the root system, arbuscular density in the colonized root fragment, and the intensity of mycorrhizal colonization in the colonized root fragments in the remediated treatments increased with time; at the end of the experiment, no consistent differences in these parameters of mycorrhizal colonization were found among the treatments. Our results suggest a restored biological functioning of the remediated soil after one year of vegetable cultivation. In general, no differences were found between the Rem and Rem+V treatments, indicating that simple common garden practices are sufficient to restore soil functioning after remediation.

The viable chelator-based soil washing has yet to be demonstrated on a larger scale. Soil containing 1850, 3830 and 21 mg kg$^{−1}$ Pb, Zn and Cd, respectively, was washed with 100 mmol EDTA kg$^{−1}$ in a series of 16 batches (1 ton soil/batch) using the new ReSoil® technology. The ReSoil® recycled the process water and 85% of the EDTA, producing no wastewater and 14.4 kg ton$^{−1}$ of waste. The soil washing removed 71, 28 and 53% of Pb, Zn and Cd, respectively, mainly from the carbonate fraction, saturated the soil with basic cations and increased the soil pH by up to 0.5 units. Raised beds (4 × 1 × 0.5 m) with original (contaminated) and remediated soil were constructed as lysmeters, and local produce was grown from July 2018 to November 2019. Throughout the gardening period, the concentration of Pb and Cd in the leachates from the remediated soil was lower and that of Zn was higher than in the original soil. Remediation decreased the concentration of plant-available and mobile toxic metals, as determined by CaCl$_2$ and NH$_4$NO$_3$ extractions, and reduced the bioavailability of Pb, Zn, and Cd in the simulated human gastrointestinal phase by an average of 4.3, 1.7 and 2.7-fold, respectively. Revitalization with vermicompost, earthworms and rhizosphere soil, and spring fertilisation with compost and manure, had no significant effect on the mobility and accessibility of the toxic metals. The ReSoil® is a cost-effective technology (material cost = 18.27 € ton$^{−1}$ soil) and showed the prospect of sustainable reuse of remediated soil.

Zone lines in wood are formed on the border of two mutually antagonistic fungi. These lines, also known as pseudosclerotial plates, owe their colour to the presence of melanin. Recently, melanin has been studied for its semiconductive properties. Melanin is also known for its ability to absorb various heavy metals. Within our study, we isolated several mutually antagonistic strains of Kretzschmaria deusta, examined the possible toxic effect of the heavy metals on the fungi by measuring growth rates, described a novel method for producing wood with zone lines with the isolated fungi, and assessed the influence of selected heavy metals on the electrical conductivity of melanin in pseudosclerotial plates. We successfully isolated five strains of K. deusta from a naturally infected log. Most of the heavy metals had a negative effect on the fungi, except iron(III) oxide, which was used in producing the final samples. The method for producing zone lines was extremely successful. We assessed that this method could be a good starting point in the development of an industrial process of spalted wood production. Due to the COVID-19 epidemic, the electrical conductivity measurements could not be performed. Na meji dveh medsebojno antagonističnih kolonij gliv se tvorijo conske linije, ki so vidne kot črne črte v notranjosti lesa. Strokovno se imenujejo pseudosklerotske plošče ali conske linije in vsebujejo melanin, ki jim daje črno obarvanje. V zadnjih desetletjih je melanin vse pogosteje raziskovan zaradi njegovih polprevodniških lastnosti. Melanin je znan po svoji zmožnosti absorbcije težkih kovin. V okviru naše raziskave smo iz narave izolirali več sevov glive Kretzschmaria deusta, ocenili učinek težkih kovin na to glivo z merjenjem hitrosti rasti, opisali novo metodo za proizvajanje vzorcev s conskimi linijami, ter kvantificirali vpliv prisotnosti težkih kovin na električno prevodnost pseudosklerotskih plošč v lesu. Uspešno smo izolirali pet sevov K. deusta iz naravno okuženega debla. Večina težkih kovin je imela negativen vpliv na rast gliv, razen železov(III) oksid, ki smo ga uporabili pri pridobivanju vzorcev s pseudosklerotskimi ploščami. Metoda za pridobivanje vzorcev je bila dosledno uspešna in ocenili smo, da bi lahko predstavljala dobro izhodišče za razvoj industrijskega postopka za pridelavo lesa s conskimi linijami. Zaradi epidemije COVID-19 meritve električne prevodnosti niso bile izvedene.

V okviru diplomskega dela smo določali vsebnost težkih kovin v površinski vodi potoka Drtijščice z namenom ocenitve njihovih vplivov na zdravje ljudi. Določali smo arzen (As), kadmij (Cd), kobalt (Co), krom (Cr), baker (Cu), molibden (Mo), nikelj (Ni), svinec (Pb), selen (Se) in cink (Zn). Terensko delo - vzorčenje smo opravili februarja 2020, takrat smo odvzeli šest vzorcev na šestih različnih odvzemnih mestih. Vzorce smo prefiltrirali in redčili z 1 % dušikovo kislino. Za določevanje kovin v vodi smo uporabili akreditirano analitsko tehniko induktivno sklopljeno plazemsko atomsko emisijsko spektroskopijo (ICP-OES), ki nam je, v enem vzorcu, omogočala določevanje več kovin hkrati. Za pripravo standardnih raztopin smo uporabili multi-standardno raztopino Merck (VI) KGaA. Dobljene koncentracije smo primerjali z mejnimi in priporočenimi vrednostmi iz domače in tuje zakonodaje ter drugimi verodostojnimi študijami. Rezultati so pokazali povišane koncentracije Se in Co, saj je vrednost teh dveh kovin v vseh šestih vzorcih presegala mejne vrednosti iz slovenske zakonodaje. Prav tako so bile na večih odvzemnih mestih presežene koncentracije Pb, As, Cd in Cu. Izmerjene vrednosti Zn in Cr v nobenem vzorcu niso presegale mejnih vrednosti. Vrednosti Mn, Mo in Ni so bile, v glavnem, pod mejo detekcije, kar pomeni, da je bila koncentracija teh kovin v vzorcih premajhna, da bi jo aparatura lahko zaznala. Povišane koncentracije skoraj polovice od preiskovanih težkih kovin v površinski vodi, nakazujejo na slabo ekološko stanje preiskovanega vodnega telesa, kar lahko vpliva na zdravje okoliških prebivalcev in vodne organizme. As part of my bachelor's degree, we determined the content of heavy metals in the surface water of Drtijščica stream in order to assess their impact on human health. In the water we determined arsenic (As), cadmium (Cd), cobalt (Co), chromium (Cr), baking (Cu), molybdenum (Mo), nickel (Ni), lead (Pb), selenium (Se) and zinc (Zn). The submitted work, i.e. sampling, was carried out in the February 2020 when six samples were taken at six different sampling points. The samples were then filtered and diluted with 1% nitric acid. For the determination of metals in water, we used the accredited method of inductively coupled plasma - optical emission spectrometry (ICP- OES), which enabled us to determine several metals in one sample simultaneously. A multi-standard solution from Merck (VI) KGaA was used to prepare the standard solutions. The results of our study were then compared with the maximum permitted and recommended concentrations from domestic and foreign legislation and other credible studies. The results showed an increased concentration of Se and Co, as the value of the two metals in all six samples exceeded the limits set by Slovenian legislation. The concentrations of Pb, As, Cd and Cu also exceeded the limit values at most of the sampling points. The measured values of Zn and Cr did not exceed the limit values in any sample. The values of Mn, Mo and Ni were mainly below the detection limit, which means that the concentration of these metals was too low for detection with the ICP- OES device. Elevated concentrations of almost half of the investigated heavy metals, indicate a poor ecological status, which can definitely have an effect on human health and aquatic organisms.

Dolgoletno onesnaževanje okolja je danes globalni problem. Zaradi človeških dejavnosti kot so industrija, rudarjenje, kmetijstvo, promet ter širjenje urbanih območij so tla močno obremenjena s težkimi kovinami. Namen naše naloge je povezan z reševanjem težav onesnaženosti Celjske kotline s težkimi kovinami. Ugotoviti smo želeli ali je možna fitoremediacija teh območij z rastlinsko vrsto prstastega trstikovca oziroma miskantusa (Miscanthus x giganteus). Leta 2015 smo s to vrsto zasadili tri načrtno izbrana onesnažena območja na vzhodnem delu Celjske kotline. Pred poskusom in po treh mesecih smo analizirali talne vzorce ter jih primerjali med seboj. Analiza talnih vzorcev je pokazala, da so tla v tem delu Celjske kotline močno obremenjena predvsem s cinkom, kadmijem in svincem. V dvotedenskem intervalnem obdobju smo spremljali različne rastne parametre sadik. Rastline so rasle na vseh treh rastiščih ne glede na tip onesnaženosti tal. Čeprav so veliko bolje uspevale v s težkimi kovinami manj onesnaženih tleh, je bila rast rastlin v močno obremenjenih tleh še vedno zelo dobra. Na najbolj onesnaženih tleh se je delež težkih kovin v tleh praviloma zmanjšal. Ugotovili smo, da ima miskantus na tem z onesnaženjem obremenjenem območju velik fitoremediacijski potencial. Today, year-long environmental pollution is a global problem. Human activity such as industry, mining, agriculture, traffic, and expansion of urban areas has resulted in heavy pollution of the soil with heavy metals. The purpose of our thesis is to resolve the problems related to the heavy metal pollution of the Celje Basin. We were looking to examine the possibilities of phytoremediation of these areas with the plant species Miscanthus x giganteus. In 2015, we planted this species in three deliberately selected polluted areas in the eastern part of the Celje Basin. We analysed the soil samples before the experiment and after three months, and compared the results. The analysis of the soil samples showed that the soil in this part of the Celje Basin is heavily polluted especially with zinc, cadmium, and lead. We monitored the various growth parameters of the seedlings across two-week intervals. The plants grew in all three planting sites, regardless of the type of soil pollution. Although they prospered better in soil with a lowed degree of heavy metal pollution, plant growth in heavily polluted soil was still very solid. In the areas with the highest degree of soil pollution, the share of heavy metal uptake by the plants was the highest. We found that the Miscanthus has great phytoremediation potential in this polluted area.

Lawsonia inermis L. znana tudi pod imenom hena, je rastlina, ki se uporablja kot naravna barva za lase, poslikavo kože in nohtov. Takšna naravna barvila lahko vsebujejo težke kovine ali toksične organske spojine v sledovih, ki ob prepogosti izpostavljenosti povzročijo škodljive učinke na zdravje ljudi. Zato je izrednega pomena določevanje nevarnih substanc v pasti oz. listih hene z zanesljivimi analiznimi metodami z zmožnostjo zaznave nizkih koncentracij preiskovanih spojin. V diplomskem delu smo določili vsebnosti štirinajstih težkih kovin v vzorcih hene z masno spektrometrijo z induktivno sklopljeno plazmo (ICP MS) in vsebnosti dveh aromatskih aminov (para-fenilendiamina in orto-fenilendiamina) s tekočinsko kromatografijo visoke ločljivosti (HPLC) z DAD detektorjem. Za analizo živega srebra smo uporabili atomsko absorpcijsko spektrometrijo (AAS), saj se pri ICP MS analizi pojavljajo prevelike motnje. Analizirali smo osem komercialno dostopnih barv, ki so bile kupljene na slovenskem tržišču in en vzorec prahu hene, brez deklaracije, kupljen na tržnici v Egiptu. V vseh vzorcih hene smo v sledovih odkrili težke kovine. Večina koncentracij težkih kovin je bila znotraj predpisanih mejnih vrednosti, ki jih predpisujejo mednarodne organizacije in vladne institucije za kozmetične izdelke ali heno. Izjema so bile koncentracije kroma, z maksimalno vrednostjo 137,01 mg/kg in koncentracije niklja, z maksimalno vrednostjo 14,49 mg/kg. Od vseh elementov smo najvišje vrednosti izmerili za aluminij v obsegu 472 mg/kg do 5907 mg/kg, za katerega sicer ni predpisanih mejnih vrednosti v kozmetičnih izdelkih ali v heni. S HPLC analizo smo ugotovili, da so v vseh analiziranih vzorcih hene vrednosti aminov pod mejo določljivosti. Lawsonia inermis L. also known as Henna, is a plant used as a natural hair, skin and nails colorant. Natural colorants derived from dried and crushed leaves may contain heavy metals and toxic organic compounds as trace elements which can pose a high risk to human health. Therefore, identifying hazardous substances in henna paste or in hena leaves is of a great importance. For analysis reliable and sensitive analytical methods that can detect low concentrations of the compounds must be used. Henna samples were analyzed to determine the contents of fourteen different heavy metals by using mass spectrometry with inductively coupled plasma (ICP MS) and to determine the contents of two aromatic amines (para-phenylendiamine and orto-phenylendiamine) with high performance liquid chromatography (HPLC) and DAD detection. Atomic absorption spectrometry (AAS) was used for the analysis of mercury since mercury causes much of interferences in ICP-MS analysis. Eight commercially available samples of henna purchased on the Slovenian market and one sample of henna purchased on a local market in Egipt were analysed. Heavy metals were detected in all samples in traces. Most of heavy metal concentrations were within the limit values prescribed by international organisations and government institutions in cosmetic products or Henna, with an exception of chromium (maximum concentration 137,01 mg/kg) and nickel (maximum concentration 14,49 mg/kg). In all of the henna samples concentrations of aluminium were higher than any other metal, ranging between 472 mg/kg and 5907 mg/kg. The results of HPLC analysis have shown that the levels of aromatic amines were under the limit of quantitation.

V magistrskem delu je predstavljena delna validacija metod z modificiranimi elektrodami kombinacij Bi-Cu na steklastem ogljiku za določanje Zn(II), Cd(II) in Pb(II). Analize smo izvajali z elektrokemijsko tehniko square wave anodno striping voltametrijo (SWASV). Dvanajst različnih elektrod smo pripravili in situ pri dveh različnih skupnih masnih koncentracijah Bi(III) in Cu(II) ter njunih različnih razmerjih v raztopini. Za vsako in situ elektrodo so bila določena območja linearnega odziva za Zn(II), Cd(II) in Pb(II), ki so morala zadoščati dvema kriterijema linearnosti: koeficientu kvalitete, QC (QC ≤ 5 %), in kvadratu korelacijskega koeficienta, R2 (R2 ≥ 0,995). Mejo zaznavnosti (LOD) in mejo določljivosti (LOQ) smo določili s pomočjo razmerja signal/šum, občutljivost pa iz naklonov umeritvene premice. Iz izkoristka pri določeni koncentraciji Zn(II), Cd(II) in Pb(II) smo določili točnost, natančnost metode in sistema pa smo določili na podlagi relativnega standardnega odmika v odstotkih (RSD [%]). Izmed vseh in situ elektrod smo na koncu izbrali dve: eno z najboljšo točnostjo (izkoristkom najbližje 100,0 %) in eno z najboljšo natančnostjo (najnižjim RSD [%]). Na obeh smo preučili vpliv interferenc in izvedli test realnega vzorca. In this master's thesis, a partial method validation with modified Bi-Cu electrodes on glassy carbon was performed for the determination of Zn(II), Cd(II) and Pb(II). Analyses were performed with an electrochemical technique square-wave anodic stripping voltammetry (SWASV). Twelve electrodes were designed in situ, at two different total mass concentrations of Bi(III) and Cu(II) and their different ratios in the solution. For every in situ electrode, a linearity for Zn(II), Cd(II) and Pb(II) were determined, which had to meet the two criteria of linearity: the quality coefficient QC had to be ≤ 5,0 % and the square of the correlation coefficient R2 had to be ≥ 0,995. Limit of detection (LOD) and limit of quantification (LOQ) were determined based on the signal-to-noise ratio, while sensitivity was determined using calibration plot slopes. Recovery at a given concentration of Zn(II), Cd(II) and Pb(II) was used to determine accuracy, while precision of the method and the system was determined on the basis of percentage relative standard deviation (RSD [%]). Among the in situ electrodes tested, two were selected to test interference effect and real sample analysis: one with the highest accuracy (recovery closest to 100,0 %) and one with the highest precision (lowest RSD [%]).

Spektroavtistične motnje (SAM) so razvojno-nevrološke motnje pri katerih opažamo občutne razlike pri spremembah v obnašanju, stereotipnem besednim in nebesednim vedenjem ter zmanjšani sposobnosti socialne interakcije. To pomeni, da je pri osebah, pri katerih se kažejo poteze diagnoze SAM, prisoten poseben in značilen vzorec vedenja in zanimanja za specifične aktivnosti. Etiologija je kompleksna in še vedno ni zadostno pojasnjena, zato vzroke še zmeraj intenzivno preiskujejo. Vse več raziskav se osredotoča na okoljske dejavnike. Izmed okoljskih dejavnikov so glede vplivov pomembne kovine, ki se v telesu pojavljajo kot elementi v sledovih. Med najbolj toksičnimi težkimi kovinami je živo srebro (Hg), ki povzroča različne poškodbe. Hg vpliva na metabolizem hemoglobina in posledično se v urinu pojavljajo različne frakcije porfirinov. Porfirinogeni se izločajo z urinom kot oksidirani porfirini, to sta uroporfirin in koproporfirin. Ključen vzrok za prekomerne vsebnosti porfirinov v človeškem urinu so zapore nekaterih encimskih poti. Težke kovine vplivajo na inhibicijo uroporfirin dekarboksilaze in koproporfirnioksidaze, kar povzroči povečanje koproporfirina in pentakarboksiporfirina v urinu. Prekoproporfirn pa nastaja in vivo iz pentakarboksiporfirinogena pod vplivom težkih kovin (Hg, Pb). V nalogi smo želeli preveriti, ali ima skupina otrok s SAM višje koncentracije celokupnih porfirinov v urinu kot kontrolna skupina otrok. Zanimalo nas je tudi, ali ima podskupina SAM, ki jo opredelimo kot skupino Aspergerjevega sindroma, višje koncentracije celokupnih porfirinov kot ostali SAM. V raziskavo smo vključili 186 otrok, od tega v skupino SAM 102 otroka, v skupino Aspergerjevega sindroma 38 otrok in v kontrolno skupino 46 otrok. Starostni razpon otrok je bil od 2–15 let. Celokupne porfirine v urinu smo določali spektrofotometrično s predhodnim odstranjevanjem interferenc na anionski izmenjevalni koloni. Rezultate smo zaradi lažje interpretacije podali na koncentracijo kreatinina. V skupini s SAM je bila povprečna vrednost celokupnih porfirinov 150,5 µg/g kreatinina (mediana 136,6 µg/g kreatinina), v skupini z Aspergerjevim sindromom 118,1 µg/g kreatinina (mediana 116,1 µg/g) in v kontrolni skupini 58,6 µg/g kreatinina (mediana 36,0 µg/g). Pri primerjavi združene skupine otrok SAM in Aspergerjevega sindroma s kontrolno skupino otrok smo ugotovili, da prihaja do statistično značilnih razlik v koncentracijah celokupnih porfirinov/kreatinina med skupinama (p

V diplomski nalogi smo na treh lokacijah (Ljubljana – Obrije, Dekani, Duplek – Johe) pridobili vzorce zemlje in česna dveh sort (´Garpek´ in ´Gardos´). Vzorce česna smo razdelili na štiri morfološke dele rastline: korenine, zeleni del, ovoj stroka in strok česna. Rezultate vsebnosti kadmija (Cd) smo primerjali med različnimi rastlinskimi deli in jih vrednotili glede na mejno vrednost za živila. Ugotavljali smo, kaj vpliva na sprejem Cd v rastlino in na katerih lokacijah je bila mejna vrednost za Cd v rastlini presežena. Primerjali smo tudi sprejem Cd glede na sorto česna. Ugotovili smo, da večja koncentracija fosforja in organske snovi v zemlji negativno vpliva na sprejem Cd v rastlino. Ugotovili smo tudi, da se koncentracija Cd v rastlini razlikuje po morfoloških delih rastline. Vsebnost kadmija v česnu se je razlikovala po lokacijah. Mejno vrednost za živila je v ovojih in koreninah presegala na vseh lokacijah obeh sort, v zelenem delu in strokih je bila mejna vrednost presežena le v Dupleku – Johe in Ljubljani – Obrije. Vsebnost Cd v sorti ´Garpek´, je bila v povprečju večja od vsebnosti v vzorcih sorte ´Gardos´, kar lahko sklepamo, da na sprejem vpliva tudi sorta česna. In the diploma thesis, we obtained soil and garlic samples of two varieties ('Garpek' and 'Gardos') at three locations (Ljubljana - Obrije, Dekani, Duplek - Johe). Garlic samples were divided into four morphological parts of the plant: the roots, the green part, the tunic of the bulb and the cloves of the garlic. The results of the cadmium content (Cd) were compared between different plant parts and evaluated against the maximum level for foodstuffs. We determined what affects the uptake of Cd into the plant and at which locations the threshold for Cd in the plant was exceeded. We also compared Cd uptake by garlic variety. Higher concentrations of phosphorus and soil organic matter were found to have a negative effect on the uptake of Cd by the plant. We also found that the concentration of Cd in the plant differs according to the morphological parts of the plant. The Cd content of garlic varied by location. The limit value for foodstuffs exceeded in all samples of tunics and roots at all locations for both varieties, in the green parts and in the cloves the limit value was exceeded only in Duplek - Johe and Ljubljana - Obrije. The Cd content of the 'Garpek' variety was, on average, higher than the content of the 'Gardos' samples, which suggests that the acceptance of the garlic varieties was also affected.

Onesnaževanje okolja s težkimi kovinami in reševanje le te problematike na učinkovit in hkrati ekonomsko sprejemljiv način, predstavlja vedno večji izziv v današnjem času. V diplomski nalogi smo preučevali adsorpcijske lastnosti bentonita za adsorpcijo kovinskih ionov (železo, baker, svinec) iz vodne raztopine. Masne koncentracije kovinskih ionov v raztopini smo določili z optično emisijsko spektroskopijo (ICP OES). Prav tako smo preučili karakteristike samega bentonita (velikost delcev, zeta potencial, specifična površina, volumen por). Karakterizacija je pokazala, da je v našem vzorcu bentonita povprečni zeta potencial - 0,257 mV in povprečna velikost delcev 1657 nm. Ugotovili smo, da s spreminjanjem pH raztopin Fe2+, Cu2+ in Pb2+ ionov, bentonit najbolje adsorbira pri pH vrednosti 7. Spreminjali smo tudi koncentracije samih raztopin z Fe2+, Cu2+ in Pb2+ ionov v območju od 1 mM do 13 mM in izmerili, da ima bentonit največjo kapaciteto pri koncentraciji 13 mM. Prav tako smo preizkusili medsebojni vpliv ionov na adsorpcijo in ugotovili, da je učinkovitost adsorpcije vseh treh ionov nad 99 %. Iz rezultatov diplomskega dela lahko sklepamo, da je bentonit odlična izbira za odstranjevanje železovih, bakrovih in svinčevih ionov iz vode. Heavy metal pollution and how to solve this problem in an efficient and economically acceptable way, represents one of the biggest problems in our modern world. In diploma thesis, we examined adsorption capacity of bentonite for the adsorption of metal ions (iron, copper, lead) from aqueous solution. The mass concentrations of the metal ions in the solution has been determinated by optical emission spectroscopy (ICP OES). Furthermore, the characteristics of bentonite (particle size, zeta potential, specific surface area, pore volume) has been examined. Characterization showed that for our sample of bentonite, the average zeta potential was 0.257 mV and the average particle size was 1657 nm. We observed that by changing the pH of Fe2+, Cu2+ and Pb2+ ion solutions, bentonite absorbs best at pH value of 7. By varying the concentration of the solutions of Fe2+, Cu2+ and Pb2+ ions in range from 1 mM to 13 mM it was found that bentonite has the highest capacity at a concentration of 13 mM. In addition, we investigated the interactions of the ions in solution and their influence on adsorption and we realised that the adsorption efficiency of all three ions was above 99 %. The results of the thesis lead to the conclusion, that bentonite is an excellent choice for the removal of iron, copper and lead ions from water.

Namen diplomske naloge je bilo s pomočjo literature preučiti vrste postopkov odstranjevanja težkih kovin iz onesnažene zemlje in možnost njihove ponovne uporabe v kmetijstvu. Odločil sem se za postopek pranja sedimenta in blata, ki smo ga pridobili iz dveh čistilnih naprav. Z eksperimentom sem poskušal določiti najprimernejši čas pranja vzorca v kelatnem sredstvu, ki je bil v našem primeru EDTA. V teoretičnem delu so opisani najpogostejši vzroki kontaminacije in posledice degradacij tal s težkimi kovinami. Prav tako so povzete lastnosti naslednjih elementov: svinec, kadmij, cink, mangan, železo, nikelj, živo srebro, arzen, kositer. Predstavljenih pa je tudi vrsto različnih postopkov oz. načinov čiščenja prsti. Eksperimentalni del sem izvedel v laboratoriju, kjer sem na začetku pripravil načrt izvedbe eksperimenta, povezanega z določevanjem količin posameznih težkih kovin v vzorcu zemlje pred in po čiščenju z EDTA. Sledil je postopek priprave vzorca, vse od vzorčenja, mletja, sejanja in sušenja. Za analizo sem imel tri različne vzorce, in sicer: sediment Drave, blato iz industrije težkih odpadkov in mulj iz čistilne naprave. Nato sem začel s postopkom pranja, tako da sem na vzorce nalili ligand EDTA in pričel z mešanjem. Po končani metodi je sledila filtracija in sušenje očiščene zemlje. Izbral sem metodo razklopa z zlatotopko in s hitrimi testi dobili vednosti težkih kovin v zemljini. Elementi kroma, železa in cinka so imeli največje vrednosti koncentracij, ki pa se je skozi daljšanje časa pranja zmanjševala. Opazil sem tudi, da je najprimernejši čas pranja pri šestih urah. The aim of this paper is to study the types of heavy metal removal processes from contaminated soil and the possibility of their re-use in agriculture. After theoretical exploration of that topic I practically researched the sediments and sludge washing process. We obtained samples from two treatment plants. With the experiment, I tried to determine the most appropriate washing time of the sample in the chelating agent, which in our case was EDTA. In theoretical part I described the most common causes of contamination and the consequences of soil degradation by heavy metals. The properties of the following elements are also explained: lead, cadmium, zinc, manganese, iron, nickel, mercury, arsenic and tin. I also explained a number of different procedures or ways of cleaning the soil. The experimental part was carried out in the laboratory. I initially prepared a plan for carrying out an experiment, which includes defining the amount of a specific heavy metal in the soil sample before and after EDTA washing. A sample preparation process followed, everything from sampling, grinding, sieving and drying. I had three different samples to analyze: Drava sediment, heavy waste sludge, and sewage sludge. I then started the washing process by pouring EDTA ligand onto the samples and started mixing. This was followed by filtration and drying of the purified soil. I chose the aqua regia method of decomposition and obtained the amount of heavy metals in the soil by rapid tests. The elements of chromium, iron and zinc had the highest values of concentrations, which decreased with time of washing. I also discover that the most appropriate time of washing is 6 hours.

S preučevanjem vzorcev las smo poskušali ugotoviti, ali obstaja bistvena razlika v vsebnosti kovin glede na onesnaženost področja, iz katerega so bili odvzeti vzorci. V ta namen smo zbrali 69 vzorcev las iz treh mest v treh različnih državah: iz Ljubljane (Slovenija), Malega Lošinja (Hrvaška) in Sarajeva (Bosna in Hercegovina). Poleg vpliva okolja smo študirali tudi kako na vsebnost kovin v laseh vplivajo naslednji dejavniki: biološka faktorja (spol in starost), kajenje in barvanje las. Celotni analizni postopek je sestavljen iz naslednjih korakov: zbiranje in skladiščenje vzorcev, pranje, sušenje, razklop in merjenje. Metodo za določanje elementne sestave las smo izbrali s pomočjo preliminarnih preiskav in literature. Zaradi nizke meje zaznave in predvsem zaradi možnosti multielementne analize smo po razklopu analizirali vzorce na ICP-MS-u in ICP-OES-u. Preden smo začeli z meritvami realnih vzorcev, smo določili še: linearnost, občutljivost, mejo zaznavnosti in določljivosti, natančnost ter pravilnost. Rezultate meritev smo statistično obdelali v SPSS-u z namenom ugotavljanja statističnih razlik med skupinami vzorcev. Statistični testi so pokazali, da biološka faktorja vplivata na vsebnost makro elementov, kot sta Ca in Mg. V primerjavi z nebarvanimi vzorci las smo statistično značilne višje koncentracije Na, Mg, Ni, Sr in Pb našli v barvanih vzorcih. Pri primerjavi krajev izvora vzorca razlike v koncentraciji toksičnih kovin niso dovolj izrazite, da bi kazale na vpliv onesnaženosti okolja s težkimi kovinami na izbrano populacijo. The aim of this study is to compare the content of heavy metals in the hair of people inhabiting three areas with different degree of pollution. 69 hair samples from three cities from three countries were selected for the analysis, that is, Ljubljana (Slovenia), Mali Lošinj (Croatia) and Sarajevo (Bosnia and Herzegovina). Environmental factors, biological factors (gender and age), smoking status and hair coloring were examined in relation to heavy metals content in the hair. The procedure consists of following steps: sample collections and storage, washing, drying, digestion and measurement. The choice of the most appropriate method is based on the previous literature review and preliminary laboratory tests. In order to perform multi-element analysis and due to low limit of detection, sample solutions were analysed by means of ICP-MS and ICP-OES methods. Before the measurement of real samples, linearity, sensitivity, limit of detection and quantification, accuracy and precision were determined for both method and instrument. Statistical analysis were carried out using SPSS statistical software. The impact of biologic factors on the concentrations of macro elements such as Ca and Mg in the hair was detected. Compared to the sample of non-colored hair, the concentrations of Na, Mg, Ni, Sr and Pb were greater in the sample of colored hair. The differences in the concentration of heavy metals in hair between three different areas were not large enough to indicate the impact of environmental pollution on heavy metals in the hair of the study sample.

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.

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.

Možnosti ravnanja z odpadnimi goščami iz komunalnih čistilnih naprav, zaradi povišane vsebnosti težkih kovin, omejuje zakonodaja. Kljub visokemu deležu organskih snovi in hranil, je njihova uporaba v kmetijstvu prepovedana. Ena izmed obetajočih naprednih metod odstranjevanja težkih kovin je adsorpcija na magnetne nanodelce, ki se jih po čiščenju odstrani z magnetno separacijo. Pri magistrskem delu smo sintetizirali in okarakterizirali tri sisteme magnetnih nanokompozitov: maghemit – L-lizin, ki so se razlikovali po načinu vezave L-lizina. Za uspešno se je izkazala le kovalentna vezava. Ta sistem je pri čiščenju vzorca mulja dosegel 37 % učinkovitost odstranitve Zn, 27 % Cr(VI) in 26 % Cu. Due to increased content of heavy metals, possibilities of waste sludge management from municipal wastewater treatment plants are limited by legislation. Despite of high content in organic substances and nutrients, sludge use in agriculture is restricted. One of the advanced methods for metal removal is adsorption on magnetic nanoparticles, which can later be removed by magnetic separation. Three systems of magnetic nanocomposites: maghemite – L-lysine, which differed in the L-lysine binding method, were synthesized and characterized. Only chemical bonding was successful. This system achieved 37, 27 and 26 % removal efficiency of Zn, Cr(VI), and Cu from a sludge sample respectively.

Onesnaževanje z odpadnimi vodami predstavlja velik delež onesnaževanja narave. V teh odpadnih vodah se pogosto nahajajo tudi težke kovine, ki jih moramo zaradi ogrožanja okolja, živali in ljudi iz vode odstraniti. Kot poceni metoda za odstranjevanje težkih kovin iz vode, se je uveljavila adsorpcija. V iskanju učinkovitih ter poceni adsorbentov, se je dobro izkazala tudi žlindra, ki je stranski produkt pri proizvodnji jekla. V diplomskem delu predstavljamo rezultate raziskave adsorpcijskih lastnosti bele žlindre. Žlindri smo najprej določili specifično površino BET, volumen por, premer por, velikost delcev in zeta potencial. Nadalje smo preučevali vpliv pH in koncentracije na adsorpcijo železovih, bakrovih in svinčevih ionov. Hkrati smo preučili še medsebojni vpliv izbranih ionov na adsorpcijo. Preučevali smo učinkovitost in kapaciteto adsorpcije in iz rezultatov ugotovili, da pH minimalno vpliva na adsorpcijo bakra in železa, svinec pa ima adsorpcijski maksimum pri pH 7. Pri preiskovanju vpliva koncentracije smo ugotovili, da učinkovitost adsorpcije s koncentracijo narašča za svinec, na baker in železo pa skoraj ne vpliva, saj je bila učinkovitost v območju koncentracij od 1 mM do 13 mM 100 %. Medsebojni vpliv ionov daje pozitivne rezultate na učinek adsorpcije. Waste water pollution represents a substantial share in environmental pollution. Quite often, waste waters contain heavy metals – and because they pose a threat to the environment, animals and humans, their removal from water is necessary. Adsorption has become a widely used and inexpensive method for removing heavy metals from water. In search for efficient and inexpensive adsorbents, slag, a steel-making by-product, has performed rather well. The present diploma thesis presents the findings of the study of white slag adsorption properties. First, specific surface area BET of slag was determined as well as pore volume, pore diameter, particle size and zeta potential. The next step was the determination of how pH and concentration affect the adsorption of iron, copper and lead ions. The interaction of the selected ions and their impact on the adsorption process was also studied. The results of adsorption efficiency and capacity reveal that the pH has minimal effect on the adsorption of copper and iron for lead the adsorption maximum is at pH 7. Higher concentrations resulted in better adsorption efficiency for lead but hardly affected the adsorption of copper and iron – the efficiency range being from 1 mM to 13 mM 100%. The interaction of ions positively affects the adsorption efficiency.

Zagotavljanje čiste in kvalitetne vode postaja problem sodobne družbe. Težke kovine so eno izmed najnevarnejših onesnaževal, saj niso biološko razgradljive, se kopičijo v naravi in toksično učinkujejo na žive organizme že pri zelo nizkih koncentracijah. V primerjavi z ostalimi metodami za odstranjevanje težkih kovin iz odpadnih vod, se je adsorpcija na različne adsorbente izkazala kot bolj ekonomična in učinkovita. Z razvojem nanotehnologije so bili magnetni nanodelci deležni pozornosti mnogih raziskav za iskanje najprimernejši adsorbentov težkih kovin. Namen diplomske naloge je bila sinteza stabilnih maghemitnih nanodelcev ter njihova funkcionalizacija s hitozanom po treh različnih metodah. Ugotoviti je bilo treba, kateri delci so najprimernejši za odstranjevanje Cr(VI) ionov iz raztopine in pri kateri pH vrednosti je adsorpcija najučinkovitejša. Maghemitne delce smo sintetizirali z metodo koprecipitacije in jih nato funkcionalizirali s hitozanom po treh različnih metodah (metoda kovalentne vezave, mikroemulzijska metoda in suspenzijska zamreževalna metoda). Delce smo dodali v raztopino z znano koncentracijo Cr(VI) ionov, da je potekla adsorpcija. Adsorpcijo smo izvedli pri treh različnih pH vrednostih (pH 3, 4 in 5) ter določili optimalno vrednost za adsorpcijo težkih kovin na posamezne magnetne nanodelce. Kvantitativno analizo Cr(VI) v raztopini po adsorpciji smo izvedli spektrofotometrijsko z 1,5- difenilkarbazidom. Po opravljeni analizi smo primerjali uspešnost adsorpcije in določili delce, ki so dosegli najvišje odstotke adsorpcije. Ugotovili smo, da so najprimernejši delci za odstranjevanje Cr(VI) iz vode maghemitni delci funkcionalizirani z mikroemulzijsko metodo. Izkazalo se je tudi, da so najboljšo adsorpcijo vsi delci dosegli pri vrednosti pH 3. Providing clean and quality water is one of the major challenges of the modern world. Heavy metals are one of the most dangerous contaminants due to their non- degradability and persistence in the environment. Heavy metals accumulate through the food chain, moreover, they can be toxic and harmful to living organisms, even in small amounts of exposure. Among numerous technologies that have been developed for the removal of heavy metals from wastewater, adsorption has been proved as one of the most economical and efficient methods. As nanotechnology is progressing rapidly, magnetic nanoparticles have been gaining increasing interest as adsorbents for heavy metals. The aim of the diploma thesis was preparation of stable maghemite nanoparticles and their functionalization with chitosan, using three different methods. The main objectives were determining which magnetic nanoparticles are the most suitable for removal of Cr(VI) and evaluating removal efficiency at different pH. Maghemite nanoparticles were synthesized by co-precipitation method and then functionalized with chitosan by three different methods (covalent binding method, microemulsion method and suspension cross-linking technique). Different nanoparticles were used as magnetic adsorbents for removal of Cr(VI) from aqueous solution. In order to determine the effect of pH on the process od adsorption, we conducted experiments at different pH value (pH 3, 4, and 5). For quantitative determination of Cr(VI) concentrations in aqueous solutions after adsorption process, we used spectrophotometric method with 1,5-diphenylcarbazide. After analysis we ascertained which magnetic nanoparticles have achieved efficient removal rates of Cr(VI). The study reveals that the maghemite nanoparticles functionalized with chitosan by microemulsion method, are most effective adsorbents for removal of Cr(VI) from aqueous solutions. All off the tested maghemite nanoparticles achieved higher removal rates with a pH value decrease.