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1.
Investigations of chemical element distributions in soil, North Macedonia—a review
Trajče Stafilov, Robert Šajn, Jasminka Alijagić, 2024, original scientific article

Abstract: This review article considers the following aspects: naturally distributed chemical elements and their enrichments, and the increased occurrence of PTEs due to anthropogenic and urban activities, as well as due to the geochemical uniqueness of certain geochemical landscapes, depending on the lithological environment. The review article is the result of many years of successful cooperation between the Geological Survey of Slovenia and the Faculty of Natural Sciences in Skopje, Ss. Cyril and Methodius University in Skopje, as well as several other institutions from North Macedonia, Russia and Romania but, also, through the voluntary and enthusiastic work of Prof. Trajče Stafilov’s PhD and Master’s students. To create the Geochemical Atlas, the territory of North Macedonia was covered with 995 sampling locations, but 16 separate areas with soil contamination were additionally sampled. The total sum of all collected soil samples was 3983 from 2449 different sampling sites in the period from 2006 to 2017. The analyses were performed at the Institute of Chemistry, Faculty of Natural Sciences in Skopje, at the Ss. Cyril and Methodius University in Skopje, North Macedonia, at the Research Institute for Analytical Instrumentation (ICIA), Cluj-Napoca, Romania, at the Joint Institute for Nuclear Research in Dubna, Moscow Region, Russia, and at Acme Labs in Vancouver, Canada. The sum of all analysed soil samples in all four mentioned laboratories was 7991 from 2006 to 2017. Using advanced mathematical methods such as multivariate statistical methods (HCA, FA, PCA) and artificial neural networks–multilayer perceptron (ANN-MP), predictions were made about the concentrations of potentially toxic elements (PTEs) and their distribution in real space. In less than two decades (2007–2023) of fruitful collaboration, a large number of scientific works have been published: 188 scientific publications, 8 geochemical atlases and 23 chapters in monographs.
Keywords: chemical elements, distribution, pollution, soil, North Macedonia
Published in DiRROS: 25.03.2024; Views: 48; Downloads: 13
.pdf Full text (86,55 MB)

2.
Moss as a biomonitor to identify atmospheric deposition of minor and trace elements in Macedonia
Robert Šajn, Katerina Bačeva Andronovska, Trajče Stafilov, Lambe Barandovski, 2024, original scientific article

Abstract: The present work was carried out to obtain and highlight the fifth comprehensive baseline dataset on atmospheric deposition of trace elements and to assess air quality in Macedonia. In the period from August to September 2020, a total of 72 moss samples were collected in accessible areas in the country. The content of 28 elements (Ag, Al, B, Ba, Ca, Cd, Co, Cr, Cu, Fe, Ga, Hg, K, La, Mg, Mn, Mo, Na, Ni, P, Pb, S, Sb, Sc, Sr, Ti, U, and Zn) was determined using inductively coupled plasma–mass spectrometry. Based on the data obtained on the content of the elements, a factor analysis was carried out to identify and characterise different sources of pollution. In addition, distribution maps were created for all elements to show the regions most affected by anthropogenic activities. The survey conducted in 2020 has shown that air pollution with potentially toxic elements (PTEs) has slightly decreased compared to the results of the previous survey from 2015. This is due to the fact that, despite the operation of all mining and smelting facilities with the same capacity, government regulations for the installation of cleaning systems and additional regulations to reduce pollution have been introduced in the last five years. Nevertheless, the fact remains that the highest anthropogenic air pollution with PTEs is still caused by the operation of the ferronickel smelter in Kavadarci (Ni and Cr) in the southern part and by the lead and zinc mines in Probištip, Makedonska Kamenica, and Kriva Palanka in the eastern part of the country (Cd, Pb, and Zn).
Keywords: moss, atmospheric deposition, trace elements, air quality, Macedonia
Published in DiRROS: 20.03.2024; Views: 54; Downloads: 19
.pdf Full text (9,64 MB)

3.
Innovative pre-fabricated components including different waste construction materials reducing building energy and minimising environmental impacts (InnoWEE)
Elena Loredana Fodor, Vilma Ducman, Giovanni Ferrarini, Sergio Tamburini, Constantinos Tsoutis, Francesca Becherini, Antonio Garrido-Marijuán,, Giulia Mezzasalma, Leonardo Rossi, Emil Lezak, Adriana Bernardi, 2019, published scientific conference contribution

Abstract: InnoWEE is a four-year project (from 2016 to 2020) financed by the European Community that involves ten partners from different European countries, as Greece, Italy, Belgium, Romania, Slovenia, Spain and Poland. The aim is to use the waste materials coming from construction and demolition processes of buildings and include them into a geopolymeric matrix with the purpose of producing prefabricated panels for different applications. Construction and demolition waste (CDW) materials with suitable characteristics have been selected to develop high performance geopolymeric panels for building walls envelopes and radiant panels for indoor walls and ceilings with low environmental impact. Field tests will be carried out in different sites in Europe characterized by different climatic conditions to check the simplicity of the installation procedure and the performance of the panels in terms of energy efficiency and environmental impact.
Keywords: prefabriced elements, geopolymers, CDW
Published in DiRROS: 08.03.2024; Views: 68; Downloads: 37
.pdf Full text (1,99 MB)
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4.
Assessment of atmospheric deposition of potentially toxic elements in Macedonia using a moss biomonitoring technique
Lambe Barandovski, Trajče Stafilov, Robert Šajn, Katerina Bačeva Andronovska, Marina V. Frontasyeva, Inga Zinicovscaia, 2024, original scientific article

Abstract: This study aims to investigate the changes in atmospheric deposition trends in Macedonia, using a moss biomonitoring technique. This technique has been used to assess the content of potentially toxic elements in Macedonia in 2002, 2005, 2010, and 2015, within the framework of the International Cooperative Program on Effects of Air Pollution on Natural Vegetation and Crops. The content of 42 elements was analyzed using instrumental neutron activation analysis (INAA), inductively coupled plasma–atomic emission spectrometry (ICP–AES), and atomic absorption spectrometry (AAS), on 72 moss samples collected in the summer of 2015. The median values of the elements studied were compared with data from previous years and with median values obtained from comparable studies in Norway and the neighboring countries. Through factor and cluster analysis, three geogenic factors were identified: Factor 1, which includes the elements Al, Ce, Fe, Hf, La, Li, Na, Sc, Sm, Tb, Ti, Th, V, and U; Factor 4, which includes As, Cl, and I; and Factor 5, which includes the elements Ba and Sr. In addition, one geogenic-anthropogenic factor containing Co, Cr, and Ni (Factor 2), was identified, and one anthropogenic factor containing Cd, Pb, Sb, and Zn (Factor 3). The lead and zinc mines near the towns of Kriva Palanka, Probištip, and Makedonska Kamenica in the eastern region of the country, the former lead and zinc smelter in the town of Veles, and the ferronickel smelter near Kavadarci, have continuously had the greatest anthropogenic impact on the atmospheric deposition of potentially toxic elements during the time period of the study. In addition to the human influences, the lithology and the composition of the soil continue to play a significant role in the distribution of the elements.
Keywords: moss, biomonitoring, air pollution, potentially toxic elements, Macedonia
Published in DiRROS: 06.02.2024; Views: 128; Downloads: 40
.pdf Full text (9,82 MB)

5.
Secondary deposits as a potential REEs source in South-Eastern Europe
Robert Šajn, Jasminka Alijagić, Ivica Ristović, 2024, original scientific article

Abstract: The main objective of this manuscript is to collect, classify, and compile all available data about secondary mineral sources of REEs in the South-Eastern Europe (SEE). The material is generated from the extracting and processing sector, that might be possibly transformed in the business process becoming an important raw material for another industry. The management inventory guide will strengthen communication and dissemination efforts and simultaneously contribute to Europe’s self-sufficiency and support transitioning to green and digital technology. Identification of the knowledge gaps associated with secondary sources of REEs in SEE will contribute to connections between all partners being involved at the beginning, during the lifetime of products and at the end of the life cycle, represented with deposit owners, technology developers and potential processors, producers, and potential users. At the investigated area it was found 1835 individual landfills, most of them belonging to waste rocks. The total quantity of all material in SRM is about 3.2 billion tons on an area of about 100 km2. The largest 95 individual landfills were selected as potential prospective landfills, containing about 1600 million tons of material. The estimated total potential of REEs (ΣREE) is more than 200 Kt. The largest quantities are found in landfills for coal fly ash and Cu flotation, which correspond to more than 80% of the ΣREE. Most of the promising sites are located in Serbia and North Macedonia. It has been calculated that the valorisation potential and perspectivity of REE2O3 is about 32.5 billion USD (prices from December 2022). According to the average concentrations of REEs, the most prospective are the red mud dams but their total volume is limited compared to massive amounts of coal fly ash landfills. The REEs content in all type of investigated materials, especially in coal fly ash in North Macedonia is twice as high as in other countries.
Keywords: secondary raw materials, ESEE, rare elements, economic prospective
Published in DiRROS: 06.02.2024; Views: 108; Downloads: 27
.pdf Full text (12,40 MB)

6.
Application of multivariate statistical methods for determining geochemical trends of elements on the territory of Slovenia
Robert Šajn, Mateja Gosar, Jasminka Alijagić, Tamara Teršič, 2024, original scientific article

Abstract: The main objective of this study is to map multi-element geochemical anomalies in soil on a regional scale. We aimed to determine and evaluate the baseline geochemical values and main geochemical trends in soil that may serve as reference values against any future changes. A total of 817 topsoil samples (0–10 cm) were collected in a 5 × 5 km grid and analyzed for 35 elements using ICP-ES after multi-acid digestions (HClO4/HNO3/HCl/HF) and 53 elements using ICP-MS after modified aqua regia digestion (HCl/HNO3/H2O). The analytical results for the two different digestion methods (multi-acid digestion vs. aqua regia) were also compared for each chemical element. Multivariate statistical methods were applied to identify the geochemical trends and main sources of trace elements over the territory of Slovenia. Based on these results, seven natural and one mixed natural/anthropogenic geochemical association were established. The contents and trends of the determined factors are presented according to 8 natural units, 4 drainage areas, and geological units characteristic of Slovenia. The identified anthropogenic geochemical association combines toxic elements (Ag, Bi, Cd, Hg, P, Pb, S, Sn, and Zn). Increased values of these elements can be found in mining areas and metallurgic centers, in Quaternary sediments of the Sava River, and Adriatic Basin as the consequence of past mining activities and in the Julian Alps, where their origin could be connected to the atmospheric deposition.
Keywords: soil, geochemical mapping, distribution of geochemical elements, factor analysis, cluster analysis
Published in DiRROS: 04.01.2024; Views: 168; Downloads: 38
.pdf Full text (9,92 MB)

7.
Heavy minerals as indicators of source material in soils on carbonates
Barbara Čeplak, Miloš Miler, Nina Zupančič, Simona Jarc, 2023, original scientific article

Abstract: The origin of the soils formed on carbonate rocks remains uncertain, as they are probably of polygenetic origin. Of particular interest are the elevated contents of some trace elements detected in these soils, as they can hardly be attributed to insoluble residues of carbonate rock. The aim of this study was to uncover the relationship between heavy minerals in bedrock and soil and to identify other sources that influence the mineral and chemical composition of soil. We investigated representative samples of soils and dolomite bedrock as well as sandstones and marlstones from the nearby flysch basin as an expected source of the aeolian contribution. XRD and SEM/EDS showed that mineral diversity is higher in soils compared to the dolomites. Heavy minerals found in dolomite insoluble residue include sphalerite, Ti-oxide (probably rutile), zircon, fluorite, pyrite, minerals of REE phosphates and apatite group, interpreted as terrigenous detrital material. The mineral composition of soil heavy fraction is only partly following insoluble residues of bedrock and indicates possible aeolian contribution. Comparison with nearby flysch sandstones and marlstones showed similarities in mineralogical diversity by the presence of chromite and Fe-Cr(Mn) oxides (probably carmichaelite). Other minerals present in soils and flysch layers, such as Ti-oxide (probably rutile), zircon, REE phosphates, and pyrite grains, however, show similarities in mode of occurrence and transport indications. Signs of aeolian transport on the grains detected in soils were further confirmed by SEM/EDS.
Keywords: Phaeozem, Upper Triassic dolomite, flysch layers, trace elements, SEM/EDS
Published in DiRROS: 04.01.2024; Views: 193; Downloads: 40
.pdf Full text (8,60 MB)

8.
Remediation of contaminated soil by red mud and paper ash
Primož Oprčkal, Ana Mladenovič, Nina Zupančič, Janez Ščančar, Radmila Milačič, Vesna Zalar Serjun, 2020, original scientific article

Abstract: Remediation of contaminated soil can be performed by using various techniques, which must be adequately tailored for each specific case. The aim of this research is to critically evaluate the potential use of red mud and paper ash and a combination of the two as immobilization additives for the remediation of contaminated soil from one of the most polluted sites in Slovenia. The proposed procedure involves the preparation of geotechnical composites made from contaminated soil and mixed with 25 wt% of immobilization additives and an optimal quantity of water to achieve consistency, at which maximum compaction according to the Proctor Compaction Test procedure can be achieved. The results reveal a positive, time-dependent trend for the immobilization of potentially toxic elements in the composite with paper ash, because of the formation of the new hydration products with potentially toxic elements. In a composite containing only red mud, potentially toxic elements were immobilized by sorption mechanisms with no general time-dependent trends. The composite with a combination of additives demonstrates the remediation characteristics of both red mud and paper ash. Using this approach excavated contaminated soil, red mud and paper ash can be successfully recycled in the proposed composites, which can be beneficially used in situ for rehabilitation of contaminated sites. Nevertheless, mobilization of some potentially toxic elements at high pHs may represent a limiting factor and has to be taken into the consideration when a combination of red mud and paper ash is used as immobilization additive.
Keywords: red mud, paper ash, contaminated soil, potentially toxic elements, geotechnical composites
Published in DiRROS: 31.08.2023; Views: 265; Downloads: 209
.pdf Full text (2,28 MB)
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9.
Analysis of the geological control on the spatial distribution of potentially toxic concentrations of As and F- in groundwater on a Pan-European scale
Elena Giménez-Forcada, Juan Antonio Luque-Espinar, María Teresa López-Bahut, Juan Grima-Olmedo, Jorge Jiménez-Sánchez, Carlos Ontiveros-Beltranena, José Angel Díaz-Muñoz, Daniel Elster, Ferid Skopljak, Denitza D. Voutchkova, Birgitte Hansen, Klaus Hinsby, Jörg Schullehner, Eline Malcuit, Laurence Gourcy, Teodóra Szőcs, Nóra Gál, Daði Þorbjörnsson, Katie Tedd, Dāvis Borozdins, Henry Debattista, Nina Rman, 2022, original scientific article

Abstract: The distribution of the high concentrations of arsenic (As) and fluoride (F-) in groundwater on a Pan-European scale could be explained by the geological European context (lithology and structural faults). To test this hypothesis, seventeen countries and eighteen geological survey organizations (GSOs) have participated in the dataset. The methodology has used the HydroGeoToxicity (HGT) and the Baseline Concentration (BLC) index. The results prove that most of the waters considered in this study are in good conditions for drinking water consumption, in terms of As and/or F- content. A low proportion of the analysed samples present HGT≥ 1 levels (4% and 7% for As and F-, respectively). The spatial distribution of the highest As and/or F- concentrations (via BLC values) has been analysed using GIS tools. The highest values are identified associated with fissured hard rock outcrops (crystalline rocks) or Cenozoic sedimentary zones, where basement fractures seems to have an obvious control on the distribution of maximum concentrations of these elements in groundwaters.
Keywords: trace elements, arsenic fluoride, groundwater, geo-hydrochemistry, spatial analysis
Published in DiRROS: 30.01.2023; Views: 949; Downloads: 199
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10.
Solid carriers of potentially toxic elements and their fate in stream sediments in the area affected by iron ore mining and processing
Saša Kos, Nina Zupančič, Mateja Gosar, Miloš Miler, 2022, original scientific article

Abstract: The potential environmental impact of historical mining and ore processing on stream sediments and water was studied in a small siderite iron ore deposit with diverse sulfide mineral paragenesis. The main aim was to characterize solid carriers of potentially toxic elements (PTEs) in stream sediments and mine waste, to understand their fate in fluvial systems. General mineralogy (X-ray powder diffraction) and individual solid PTE carriers (scanning electron microscopy/energy dispersive spectroscopy) were correlated with the geochemical composition of stream sediments, mine waste, and stream waters (inductively coupled plasma mass spectrometry). Primary solid PTE carriers were pyrite, chalcopyrite, sphalerite, Hg-bearing sphalerite, galena, and siderite. Slightly alkaline and oxidizing conditions in stream water promoted the transformation of primary phases into secondary PTE carriers. Fe(Mn)-oxide/oxyhydroxides were major sinks for Pb, Zn, and As. Compared to background levels, Co (14.6 ± 2.1 mg/kg), Cu (30 ± 2.9 mg/kg), Ni (32.1 ± 2.9 mg/kg), Pb (64.5 ± 16.4 mg/kg), Zn (175.3 ± 22.5 mg/kg), As (81.1 ± 63.7 mg/kg), and Hg (2 ± 0.8 mg/kg) were elevated in mining area. Mine waste contained similar PTE carriers as stream sediments, but much higher PTE contents. Prevailingly low PTE concentrations in streams, with the exception of As (1.97 ± 2.4 µg/L) and Zn (4.5 ± 5.7 µg/L), indicate the stability of PTE carriers. Environmental effects were not significant, and additional monitoring is recommended.
Keywords: environmental mineralogy, environmental geochemistry, potentially toxic elements, stream sediments, solid phases, iron ore deposit, SEM/EDS
Published in DiRROS: 16.11.2022; Views: 517; Downloads: 165
.pdf Full text (8,07 MB)

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