1. Oral bioaccessibility of potentially toxic elements in various environmental mediaMartin Gaberšek, Mateja Gosar, 2024, izvirni znanstveni članek Povzetek: An important aspect of geochemical studies is determining health hazard of potentially toxic elements (PTEs). Key information on PTEs behaviour in the human body in case of their ingestion is provided with the use of in vitro bioaccessibility tests. We analysed and compared oral bioaccessibility of a wide range of PTEs (As, Cd, Ce, Cr, Cu, Hg, La, Li, Ni, Pb, Sb, Sn, Zn), including some that are not often studied but might pose a human health hazard, in soil, attic dust, street dust, and household dust, using Unified BARGE Method (UBM). Additionally, feasibility of usage of scanning electron microscope techniques in analyses of solid residuals of UBM phases was tested. Results show that bioaccessible fractions (BAFs) of PTEs vary significantly between individual samples of the same medium, between different media and between the gastric and gastro-intestinal phases. In soil, attic dust and street dust, bioaccessibility of individual PTE is mostly higher in gastric than in gastro-intestinal phase. The opposite is true for PTEs in household dust. In all four media, with the exception of Pb in household dust, among the most bioaccessible PTEs in gastric phase are Cd, Cu, Pb, and Zn. During the transition from the stomach to small intestine, the mean BAFs of most elements in soil, attic dust, and street dust decreases. The most bioaccessible PTEs in gastro-intestinal phase are Cu, Cd, Ni, and As. Micromorphological and chemical characterisation at individual particle level before and after bioaccessibility test contribute significantly to the understanding of oral bioaccessibility. Ključne besede: urban geochemistry, UBM, soil, attic dust, street dust, household dust Objavljeno v DiRROS: 10.07.2024; Ogledov: 114; Prenosov: 65
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2. Vsebnosti potencialno strupenih elementov v sedimentih in vodah reke Meže in njenih pritokov, ki odvodnjavajo odlagališča rudarskih odpadkovMateja Gosar, Špela Bavec, Miloš Miler, Martin Gaberšek, 2024, izvirni znanstveni članek Povzetek: Predstavljeni so rezultati spremljanja vsebnosti potencialno strupenih elementov (PSE) v sedimentih (v letih 2013, 2017, 2020) in vodah (v letih 2017, 2020) reke Meže ter njenih pritokov, ki odvodnjavajo odlagališča rudarskih odpadkov. Skupno 13 vzorčnih mest je vzpostavljenih v vzorčni shemi, ki omogoča dolgoročno opazovanje vpliva odlagališč rudarskih odpadkov. V sedimentih so zaradi vplivov več kot 300-letnega delovanja rudarsko-predelovalne industrije močno povečane vsebnosti PSE, predvsem Pb, Zn, Cd, Mo in As, ki s časom precej nihajo. Razlike v vsebnostih na istih lokacijah v različnih letih so najbolj izrazite v pritokih reke Meže, ki drenirajo odlagališča rudarskih odpadkov. Na vsebnosti imajo pomemben vpliv hidrološki pogoji, saj so ob višjem vodostaju in višjem pretoku vsebnosti PSE večje. Vodna erozija odlagališč ima pomemben vpliv na dotok onesnaženega materiala v vodotoke. V nasprotju s pritoki, v zgornjem toku reke Meže nismo opazili večjega vpliva višjega vodostaja in pretoka na vsebnosti PSE v sedimentih. Dolvodno od Žerjava so nihanja vsebnosti med posameznimi leti oz. različnimi hidrološkimi pogoji tudi v Meži večja. Predstavljeni rezultati kažejo, da so v sedimentih reke Meže in njenih pritokov vsebnosti Pb, Zn, Cd, Mo in As zelo velike ter krepko presegajo zakonsko določeno kritično vrednost za tla. V površinski vodi so vsebnosti PSE lokalno povečane in se s časom bistveno ne spreminjajo. Glede na primerjavo z zakonodajnimi smernicami, so v obravnavanih vodah lokalno presežene koncentracije Pb, Cd in Zn. Ocenjujemo, da je dinamika obremenjenosti sedimentov reke Meže s PSE vzdolž krajev Črna na Koroškem, Žerjav in Mežica zelo kompleksna. Poleg odlagališč rudarskih odpadkov na vsebnosti PSE v sedimentih in vodah vplivajo tudi razpršeni viri v okolju, kot so onesnažena tla in poplavne ravnice ter njihova različna stopnja onesnaženosti, saj je okolje obremenjeno zaradi dolgoletnih rudarskih in talilniških dejavnosti. Dodaten okoljski vpliv ima morda tudi sedanja industrijska dejavnost v dolini reke Meže. Ključne besede: rudarjenje, rudarski odpadki, odlagališča odpadkov, potencialno strupeni elementi, rečni sedimenti, monitoring, onesnaženje okolja Objavljeno v DiRROS: 09.07.2024; Ogledov: 136; Prenosov: 82
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3. Characterization of atmospheric deposition as the only mineral matter input to ombrotrophic bogValentina Pezdir, Martin Gaberšek, Mateja Gosar, 2022, izvirni znanstveni članek Povzetek: Ombrotrophic peatlands contain a very small percentage of mineral matter that they receive exclusively from atmospheric deposition. Mineral matter deposited on the Šijec bog was characterized using scanning electron microscopy coupled with energy dispersive spectroscopy (SEM/EDS). We collected solid atmospheric deposition from snow, rainwater, and using passive samplers. Samples were collected at average atmospheric conditions and after two dust events. Size, morphology, and chemical composition of individual particles were determined. We distinguished four main particle groups: silicates, carbonates, organic particles, and Fe-oxyhydroxides. Silicate particles are further divided into quartz and aluminosilicates. Proportions of these groups vary between samples and between sample types. In all samples, silicate particles predominate. Samples affected by dust events are richer in solid particles. This is well observed in passive deposition samples. Carbonates and organic particles represent smaller fractions and are probably of local origin. Iron-oxyhydroxides make up a smaller, but significant part of particles and are, according to their shape and chemical composition, of both geogenic and anthropogenic origin. Estimated quantity and percentage of main groups vary throughout the year and are highly dependent on weather conditions. Dust events represent periods of increased deposition and contribute significantly to mineral matter input to peatlands. Ključne besede: atmospheric deposition, SEM/EDS, mineral matter, peatland Objavljeno v DiRROS: 08.09.2022; Ogledov: 761; Prenosov: 354
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4. Attic dust: an archive of historical air contamination of the urban environment and potential hazard to health?Martin Gaberšek, Michael J. Watts, Mateja Gosar, 2022, izvirni znanstveni članek Povzetek: A comprehensive study of attic dust in an urban area is presented. Its entire life cycle, from determining historical emission sources to recognising the processes that take place in attic dust and its potential to impact human health is discussed. Its chemical composition and morphological characteristics of individual solid particles reflect past anthropogenic activities. High levels of Be-Cd-Cu-Sb-Sn-Pb-Te-Zn and occurrence of Cu-Zn shavings are typical for an industrial zone characterised by a foundry and a battery factory. High levels of Co-Fe-Mo-Ni-W-Ba-Cr-Mg-Mn-Nb-Ti and occurrence of various solid Fe-oxides, particularly spherical particles, were identified in another industrial zone, which was dominated by the automotive and metal-processing industries. Emissions from coal combustion affected the distribution of S-Se-Hg-Tl-As-Ag-U. The predominant mineral in attic dust is gypsum, which was presumably formed in situ by the reaction of carbonate dust particles and atmospheric SO2 gas. The high oral bioaccessibility of As-Cd-Cu-Pb-Zn in the gastric phase and high bioaccessibility of As-Cu-Cd-Ni in the gastrointestinal phase were identified. Determined characteristics of attic dust and identified possibilities of prolonged human exposure to it indicate that attic dust should be treated as an excellent proxy for historical air contamination as well as a potentially hazardous material for human health. Ključne besede: multi-element composition, scanning electron microscopy, oral bioaccessibility, unified BARGE method, urban geochemistry Objavljeno v DiRROS: 23.06.2022; Ogledov: 774; Prenosov: 289
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5. Celostna obravnava geokemije trdnih anorganskih delcev v urbanem okoljuMartin Gaberšek, 2020, doktorska disertacija Povzetek: Biogeokemično kroženje elementov je v urbanih okoljih zaradi velikega števila prebivalcev in njihovih različnih dejavnosti precej drugačno kot v naravnih. Zaradi kompleksnosti urbanih okolij, je pri geokemičnih raziskavah treba uporabiti celosten pristop. To pomeni, da s kombinacijo različnih metod preučujemo vsebnosti in pojavljanje potencialno strupenih elementov (PSE) v več urbanih materialih. V okviru doktorske disertacije smo na urbanem območju Maribora raziskovali tla, podstrešni, stanovanjski in cestni prah ter trdne delce nakopičene v snegu in delce v zraku. Opredelili smo lastnosti obravnavanih materialov in geokemične značilnosti Maribora ter vpeljali analizo trdnih delcev v zraku s SEM/EDS. Prevladujoč mineral v tleh je kremen (geogen vpliv), v cestnem prahu dolomit (zimsko posipanje cest) in v podstrešnem prahu sadra, ki je najverjetneje sekundarnega nastanka. Analiza vsebnosti 65 elementov v tleh in vseh treh tipih prahov je pokazala, da se ti materiali po kemični sestavi medsebojno močno razlikujejo. Prevladujoč antropogen izvor smo v vseh materialih, z izjemo stanovanjskega prahu, pripisali Cd, Cu, Pb, Sb, Sn in Zn. Dodatno so v posameznih materialih pretežno antropogenega izvora še nekateri drugi PSE. Na dveh industrijskih območjih (Melje in Tezno) so vsebnosti PSE običajno najvišje, zato predvidevamo, da so večinoma posledica pretekle in sedanje kovinske industrije. V primerjavi s tlemi, so vsebnosti PSE višje v prahovih, kar je deloma posledica razlik v njihovem nastanku in v fizikalno-kemičnih lastnostih, vpliva antropogenih virov ter različnega zadrževalnega časa materialov. Podstrešni prah odraža zgodovinske vplive, cestni prah predvsem današnje vplive industrije in prometa ter stanovanjski prah vplive znotraj stanovanj. Z analizo prahov in delcev v snegu ter zraku s SEM/EDS smo ugotovili, da izmed delcev s PSE v vseh materialih prevladujejo oglati Fe-oksidi. Samo na industrijskem območju Melje se pojavljajo Cu-Zn ostružki, ki najverjetneje izvirajo iz livarne in Fe-Cr (Cu, Mn, Ni) ostružki, najverjetneje iz tovarne kovinskega pohištva ter livarne. Za Tezno so značilni predvsem visoki deleži Fe-oksidov in kroglastih Fe-oksidov, pogosto z nizkimi vsebnostmi Mn in drugih PSE. Glede na rezultate, kemična sestava stanovanjskega prahu odraža predvsem vire znotraj stanovanj in manj zunanje vplive. Izmed notranjih virov smo najbolj jasno prepoznali uporabo vžigalnikov v stanovanjih v katerih stanovalci kadijo, kar se odraža v visokih vsebnostih Ce, Fe in La ter pojavljanju Fe-Ce-La-O kroglic. Biodostopni deleži (BAF) PSE se močno razlikujejo med različnimi elementi, vzorci in materiali. V tleh, cestnem in podstrešnem prahu so večinoma večji v želodčni fazi kot v želodčno-črevesni. Za stanovanjski prah velja obratno. Med najbolj biodostopnimi PSE v želodčni fazi so Cd, Cu, Pb in Zn, katerih povprečni BAF je pogosto nad 40 %, ter v želodčno-črevesni As, Cd, Cu in Ni. Ključne besede: urbana geokemija, trdni delci, potencialno strupeni elementi, biodostopnost, tla, podstrešni prah, stanovanjski prah, cestni prah, SEM/EDS Objavljeno v DiRROS: 03.03.2022; Ogledov: 1325; Prenosov: 413
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6. Preparation and characterization of the sulfur-impregnated natural zeolite clinoptilolite for Hg(II) removal fromaqueous solutionsMarin Ugrina, Martin Gaberšek, Aleksandra Daković, Ivona Nuić, 2021, izvirni znanstveni članek Povzetek: Sulfur-impregnated zeolite has been obtained from the natural zeolite clinoptilolite by chemical modification with Na2S at 150 °C. The purpose of zeolite impregnation was to enhance the sorption of Hg(II) from aqueous solutions. Chemical analysis, acid and basic properties determined by Bohem’s method, chemical behavior at different pHo values, zeta potential, cation-exchange capacity (CEC), specific surface area, X-ray powder diffraction (XRPD), scanning electron microscopy with energy-dispersive X-ray analysis (SEM-EDS), Fourier transform infrared spectroscopy (FTIR), as well as thermogravimetry with derivative thermogravimetry (TG-DTG) were used for detailed comparative mineralogical and physico-chemical characterization of natural and sulfur-impregnated zeolites. Ključne besede: zeolit, klinoptilolit, živo srebro, onesnaženje okolja Objavljeno v DiRROS: 03.03.2022; Ogledov: 835; Prenosov: 332
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7. Towards a holistic approach to the geochemistry of solid inorganicparticles in the urban environmentMartin Gaberšek, Mateja Gosar, 2021, izvirni znanstveni članek Povzetek: Airborne particulate matter (PM) has a major impact on the biogeochemical cycles of chemical elements in theurban environment. Anthropogenic-derived PM emissions are the cause of some of the most severe environmen-tal and health problems. The presented study aims to improve our knowledge of PM dynamics by introducing amulti-media, multi-analytical and multi-elemental holistic approach to geochemical studies of inorganic PM inthe urban environment. The importance of the holistic approach is highlighted and its application in a casestudy of Maribor (Slovenia) is presented. The chemical composition and individual particulate characteristicsof street, attic and household dust were determined and compared with the characteristics of airborne PM,and PM deposited in snow, together with the chemical composition of the soil. We found that the mineralogicaland chemical composition and the individual solid particle characteristics of the studied media differ consider-ably. Nevertheless, minerals of geogenic origin are present in all media. The highest levels of potentially toxic el-ements (PTEs) in all media, except household dust, are typical for industrial areas. Street dust primarily reflectsthe influence of winter road maintenance and industrial activities, while characteristics of household dust arepredominantly influenced by indoor activities and properties of dwellings. The comparison of the chemical com-position of attic and street dust indicates that emissions of As, Cd, Pb, S and Zn were higher in the past. The char-acterisation of airborne PM and PM deposited in snow is essential for the identification of the mostrecentsourcesof PTE-bearing particles. Several industrial sources and the fate of some particle types in the environment havebeen determined based on thefindings of the SEM/EDS analyses. This study confirms that various environmentalmedia are carriers of diverse geochemical information and highlights the importance of a holistic approach ingeochemistry of PM in urban areas. Ključne besede: Street dust, attic dust, household dust, airborne particulate matter, potentially toxic elements, SEM/EDS Objavljeno v DiRROS: 06.01.2021; Ogledov: 1928; Prenosov: 890
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