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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: 16
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2.
Extreme environments simplify reassembly of communities of arbuscular mycorrhizal fungi
Nataša Šibanc, Dave R. Clark, Thorunn Helgason, Alex J. Dumbrell, Irena Maček, 2024, original scientific article

Abstract: The ecological impacts of long-term (press) disturbance on mechanisms regulating the relative abundance (i.e., commonness or rarity) and temporal dynamics of species within a community remain largely unknown. This is particularly true for the functionally important arbuscular mycorrhizal (AM) fungi; obligate plant-root endosymbionts that colonize more than two-thirds of terrestrial plant species. Here, we use high-resolution amplicon sequencing to examine how AM fungal communities in a specific extreme ecosystem—mofettes or natural CO2 springs caused by geological CO2 exhalations—are affected by long-term stress. We found that in mofettes, specific and temporally stable communities form as a subset of the local metacommunity. These communities are less diverse and dominated by adapted, “stress tolerant” taxa. Those taxa are rare in control locations and more benign environments worldwide, but show a stable temporal pattern in the extreme sites, consistently dominating the communities in grassland mofettes. This pattern of lower diversity and high dominance of specific taxa has been confirmed as relatively stable over several sampling years and is independently observed across multiple geographic locations (mofettes in different countries). This study implies that the response of soil microbial community composition to long-term stress is relatively predictable, which can also reflect the community response to other anthropogenic stressors (e.g., heavy metal pollution or land use change). Moreover, as AM fungi are functionally differentiated, with different taxa providing different benefits to host plants, changes in community structure in response to long-term environmental change have the potential to impact terrestrial plant communities and their productivity
Keywords: arbuscular mycorrhiza, elevated CO2, long-term experiments, soil biodiversity, soil hypoxia, next-generation sequencing, NGS
Published in DiRROS: 28.02.2024; Views: 97; Downloads: 49
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3.
Multivariate statistical methods in determining the spatial distribution of chemical elements in soil from the Mavrovo-Rostuše region, North Macedonia
Trajče Stafilov, Robert Šajn, Kristina Petrovska, 2023, original scientific article

Abstract: In this work, the contents and spatial distributions of 19 elements (Ag, Al, B, Ba, Ca, Cr, Cu, Fe, K, Li, Mg, Mn, Na, Ni, P, Pb, Sr, V, Zn) in the soil of the western part of North Macedonia (Mavrovo-Rostuše region) are presented. For this purpose, a total of 66 soil samples were collected from 33 locations (33 samples of topsoil, 0-5 cm, and 33 samples of subsoil, 20-30 cm). All samples were analysed by inductively coupled plasma - atomic emission spectrometry (ICP-AES) after complete digestion with four acids (HNO3, HF, HClO4 and HCl). The obtained results were statistically evaluated and spatial distribution maps for all analysed elements were also prepared. Factor analysis was performed to reduce the number of data used and new synthetic variables (factors) were identified. Through the application of factor analysis, three geochemical associations were identified: Factor 1 (Zn, K, Cu, Fe, and Li), Factor 2 (Cr, Ni, and Mg) and Factor 3 (Ca and Al). From the obtained data and the maps of spatial distribution, it could be concluded that the distribution of the analysed elements is related to the lithology of the region. Thus, it was found that the higher content of elements of Factor 1 occurs in the eastern and southern part of the study area (middle and lower reaches of the Radika River and along the Mala River), where Mesozoic and Paleozoic carbonates as well as Paleozoic shales and Paleogene flysch prevail. Factor 2 (Cr, Ni and Mg) also represents a lithogenic association. The highest contents of the elements in both soil layers were found in the areas where Paleozoic sandstones and shales (village of Lazaropole and the area around the Mavrovo Lake) and Paleogene flysch (Rostuše village) predominate. Factor 3 (Ca and Al) also represents lithogenic association of elements. The highest content of these elements was found in the northwestern part of the study area (village of Žirovnica and along the Berička River) and in the northeastern region above the village of Brodec where Mesozoic carbonates and Paleogene flysch dominate.
Keywords: soil, heavy metals, spatial distribution, Mavrovo-Rostuše region, North Macedonia
Published in DiRROS: 04.01.2024; Views: 173; Downloads: 41
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4.
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)

5.
The LANDSUPPORT geospatial decision support system (S-DSS) vision : operational tools to implement sustainability policies in land planning and management
Fabio Terribile, Marco Acutis, Antonella Agrillo, Erlisiana Anzalone, Sayed Azam-Ali, Marialaura Bancheri, Peter Baumann, Barbara Birli, Antonello Bonfante, Marco Botta, Mitja Ferlan, Jernej Jevšenak, Primož Simončič, Mitja Skudnik, 2023, original scientific article

Abstract: Nowadays, there is contrasting evidence between the ongoing continuing and widespread environmental degradation and the many means to implement environmental sustainability actions starting from good policies (e.g. EU New Green Deal, CAP), powerful technologies (e.g. new satellites, drones, IoT sensors), large databases and large stakeholder engagement (e.g. EIP-AGRI, living labs). Here, we argue that to tackle the above contrasting issues dealing with land degradation, it is very much required to develop and use friendly and freely available web-based operational tools to support both the implementation of environmental and agriculture policies and enable to take positive environmental sustainability actions by all stakeholders. Our solution is the S-DSS LANDSUPPORT platform, consisting of a free web-based smart Geospatial CyberInfrastructure containing 15 macro-tools (and more than 100 elementary tools), co-designed with different types of stakeholders and their different needs, dealing with sustainability in agriculture, forestry and spatial planning. LANDSUPPORT condenses many features into one system, the main ones of which were (i) Web-GIS facilities, connection with (ii) satellite data, (iii) Earth Critical Zone data and (iv) climate datasets including climate change and weather forecast data, (v) data cube technology enabling us to read/write when dealing with very large datasets (e.g. daily climatic data obtained in real time for any region in Europe), (vi) a large set of static and dynamic modelling engines (e.g. crop growth, water balance, rural integrity, etc.) allowing uncertainty analysis and what if modelling and (vii) HPC (both CPU and GPU) to run simulation modelling ‘on-the-fly’ in real time. Two case studies (a third case is reported in the Supplementary materials), with their results and stats, covering different regions and spatial extents and using three distinct operational tools all connected to lower land degradation processes (Crop growth, Machine Learning Forest Simulator and GeOC), are featured in this paper to highlight the platform's functioning. Landsupport is used by a large community of stakeholders and will remain operational, open and free long after the project ends. This position is rooted in the evidence showing that we need to leave these tools as open as possible and engage as much as possible with a large community of users to protect soils and land.
Keywords: land degradation, land management, soil, spatial decision support system, sustainability
Published in DiRROS: 13.11.2023; Views: 313; Downloads: 155
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6.
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
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7.
8.
Environmental impacts and immobilization mechanisms of cadmium, lead and zinc in geotechnical composites made from contaminated soil and paper-ash
Marija Đurić, Primož Oprčkal, Vesna Zalar Serjun, Alenka Mauko Pranjić, Janez Ščančar, Radmila Milačič, Ana Mladenovič, 2021, original scientific article

Abstract: Paper-ash is used for remediation of heavily contaminated soils with metals, but remediation efficiency after longer periods has not been reported. To gain insights into the mechanisms of immobilization of cadmium (Cd), lead (Pb), and znic (Zn), a study was performed in the laboratory experiment in uncontaminated, artificially contaminated, and remediated soils, and these soils treated with sulfate, to mimic conditions in contaminated soil from zinc smelter site. Remediation was performed by mixing contaminated soil with paper-ash to immobilize Cd, Pb, and Zn in the geotechnical composite. Partitioning of Cd, Pb, and Zn was studied over one year in seven-time intervals applying the sequential extraction procedure and complementary X-ray diffraction analyses. This methodological approach enabled us to follow the redistribution of Cd, Pb, and Zn over time, thus, to studying immobilization mechanisms and assessing the remediation efficiency and stability of newly formed mineral phases. Cd, Pb, and Zn were effectively immobilized by precipitation of insoluble hydroxides after the addition of paper-ash and by the carbonization process in insoluble carbonate minerals. After remediation, Cd, Pb, and Zn concentrations in the water-soluble fraction were well below the limiting values for inertness: Cd by 100 times, Pb by 125 times, and Zn by 10 times. Sulfate treatment did not influence the remediation efficiency. Experimental data confirmed the high remediation efficiency and stability of insoluble Cd, Pb, and Zn mineral phases in geotechnical composites.
Keywords: cadmium, lead, zinc, contaminated soil, paper ash, immobilization mechanisms
Published in DiRROS: 04.07.2023; Views: 302; Downloads: 196
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9.
Evasion of gaseous elemental mercury from forest and urban soils contaminated by historical and modern ore roasting processes (Idrija, Slovenia)
Federico Floreani, Elena Pavoni, Mateja Gosar, Stefano Covelli, 2023, original scientific article

Abstract: Considerable amounts of gaseous elemental mercury (Hg0) can be released into the atmosphere from Hg-enriched substrates, such as those from former mining areas, posing a potential environmental threat. In this work, Hg0 fluxes at the soil–air interface under natural vegetation covers were measured in various locations within the Idrija Hg mining area (Slovenia) and its surroundings. Sites were selected in order to compare Hg0 fluxes from both forest soils heavily impacted by historical ore roasting and urban soils characterised by a different degree of Hg enrichment due to the natural occurrence of Hg in rocks or recent mining and roasting processes. Replicate measurements at each site were conducted using a non-steady state flux chamber coupled with a real-time Hg0 analyser (Lumex RA-915M). Moreover, topsoil samples (0–2 cm) were analysed for Hg total concentration and speciation. Cinnabar was the predominant Hg form in almost all the sites. Despite Hg0 being undetectable in soils using thermo-desorption, substantial emissions were observed (70.7–701.8 ng m−2 h−1). Urban soils in a naturally enriched area showed on average the highest Hg0 fluxes, whereas relatively low emissions were found at the historical roasting site, which is currently forested, despite the significantly high total Hg content in soils (up to 219.0 and 10,400 mg kg−1, respectively). Overall, our findings confirm that shading by trees or litter may effectively limit the amount of Hg0 released into the atmosphere even from extremely enriched soils, thus acting as a natural mitigation.
Keywords: legacy soil contamination, Hg mining, gaseous Hg fluxes, flux chamber, ore roasting, Hg speciation
Published in DiRROS: 30.06.2023; Views: 372; Downloads: 103
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10.
Causes and consequences of large-scale windthrow on the development of fir-beech forests in the Dinaric mountains
Matjaž Čater, Ajša Alagić, Mitja Ferlan, Jernej Jevšenak, Aleksander Marinšek, 2023, original scientific article

Abstract: We investigated several aspects of windthrow that are relevant to our understanding and management of forest ecosystems. As an example, we used an extreme event in December 2017, when the strongest storm in recent history occurred in the Slovenian Dinaric High Karst. We examined influential factors such as soil properties, wind speed, precipitation and ecological consequences for the affected forests. Soil properties were measured around standing and fallen silver fir trees at all three research sites. Tree species composition in the regeneration was observed on plots with chemical and acoustic ungulate deterrents and on control plots without deterrents. Economic estimates of yield loss due to damage were calculated at the national level. A model of the potential threat from windthrow was also developed based on data collected from windthrow events and meteorological data over the past 20 years. Our results indicate that soil depth and mineral fraction depth were similar at sites with and without damaged trees and were not the determining factors for tree toppling. Plots with acoustic deterrents showed the most effective regeneration development, the least decline in silver fir and the greatest increase in noble hardwood seedlings, while plots with chemical deterrents showed the least browsing damage. The estimated economic loss of €16.1 million is 6.6% less than the harvest under normal conditions. The economic loss was relatively low due to the nature of the storm, with the predominant type of damage being uprooted trees with no damaged trunks. The windthrow hazard model revealed that a large number of consecutive events with strong winds in each section weakened the stand, which was subsequently knocked down during the next extreme wind and rainfall event.
Keywords: natural forest regeneration, windthrow, economic loss, browsing, ungulate deterrents, forest soil properties, potential threat model
Published in DiRROS: 27.06.2023; Views: 1059; Downloads: 505
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