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Investigations of chemical element distributions in soil, North Macedonia—a review
Trajče Stafilov, Robert Šajn, Jasminka Alijagić, 2024, izvirni znanstveni članek

Povzetek: 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.
Ključne besede: chemical elements, distribution, pollution, soil, North Macedonia
Objavljeno v DiRROS: 25.03.2024; Ogledov: 105; Prenosov: 73
.pdf Celotno besedilo (86,55 MB)

Contaminant trends in urban groundwater: case study from Ljubljana (central Slovenia)
Janja Svetina, Joerg Prestor, Brigita Jamnik, Primož Auersperger, Mihael Brenčič, 2024, izvirni znanstveni članek

Povzetek: Urban areas can significantly alter the quality status of aquifers if appropriate strategies to prevent and detect groundwater contamination are not implemented in time. The prevention of groundwater contamination should be a priority due to its potential long-term impact on the environment and the high cost of remediation. For effective and sustainable groundwater management, it is crucial to proactively monitor a wide range of compounds to prevent their spread, progression and increasing concentrations. This study is one of the few to analyse the trends of various urban groundwater contaminants (nitrate, sulphate, hexavalent chromium, pesticides, PCE and TCE) from a groundwater management perspective. Characteristic trends are assessed using linear regression and the Mann–Kendall method, while significant changes in trends are determined using the Darken and Pettitt tests. The time span of the analysed trends covers the transition period before and after the implementation of the Water Framework Directive (2000/60/EC) and the Groundwater Directive (2000/60/EC). This study confirms the effectiveness of enforcement measures to protect groundwater quality, as evidenced by several statistically significant decreasing trends. On the other hand, this study emphasises the importance of intervention-targeted sampling campaigns and the reporting of raw analytical values according to the ISO 11843 series of standards. This approach is essential to detect upward trends in emerging contaminants at an early stage and prevent them from reaching levels that could negatively impact the economy or even jeopardise the safety of drinking water supplies.
Ključne besede: groundwater contamination, contaminant trends, groundwater management, urban aquifer, Ljubljansko polje
Objavljeno v DiRROS: 25.03.2024; Ogledov: 90; Prenosov: 31
.pdf Celotno besedilo (7,36 MB)

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, izvirni znanstveni članek

Povzetek: 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).
Ključne besede: moss, atmospheric deposition, trace elements, air quality, Macedonia
Objavljeno v DiRROS: 20.03.2024; Ogledov: 81; Prenosov: 31
.pdf Celotno besedilo (9,64 MB)

Influence of geology, hydrogeology, and climate on ground source heat pump distribution in Slovenia and selected European countries
Simona Adrinek, Mitja Janža, Rao Martand Singh, 2024, izvirni znanstveni članek

Povzetek: Shallow geothermal energy (SGE) is a renewable energy that could contribute to the decarbonatization of the heating and cooling sector. SGE is predominantly harnessed through ground source heat pump (GSHP) systems. The choice of which type of GSHP system depends on various factors. Understanding these factors is crucial for optimizing the efficiency of GSHP systems and fostering their implementation. In this paper, we have analysed the spatial distribution of GSHPs in Slovenia. We identified 1073 groundwater and 1122 ground-coupled heat pump systems with a total heat pump capacity of almost 30 MW. We quantitatively assessed the influence of geological, hydrogeological, and climate conditions on their spatial distribution. Using the χ2 test and information value method, we identified hydrogeological conditions as the most influential factor for the GSHP systems’ spatial distribution. We also performed the spatial analysis of geological and hydrogeological data in 22 European countries, including Slovenia. We collected the reported numbers of installed GSHP units in 2020 and were able to distinguish the shares of groundwater and ground-coupled heat pump systems for 12 of these countries. The analysis showed that ground-coupled heat pumps predominate in most countries, even if the natural conditions are favourable for groundwater heat pumps.
Ključne besede: shallow geothermal energy, renewable heating and cooling, ground-source heat pump, spatial distribution, natural condition
Objavljeno v DiRROS: 19.03.2024; Ogledov: 75; Prenosov: 39
.pdf Celotno besedilo (15,39 MB)

Seismogenic depth and seismic coupling estimation in the transition zone between Alps, Dinarides and Pannonian Basin for the new Slovenian seismic hazard model
Polona Zupančič, Barbara Šket Motnikar, Michele M. C. Carafa, Petra Jamšek Rupnik, Mladen Živčić, Vanja Kastelic, Gregor Rajh, Martina Čarman, Jure Atanackov, Andrej Gosar, 2024, izvirni znanstveni članek

Povzetek: Seismogenic depth and seismic coupling are important inputs into seismic hazard estimates. Although the importance of seismic coupling is often overlooked, it significantly impacts seismic hazard results. We present an estimation of upper and lower seismogenic depth and expected hypocentral depth and seismic coupling in the transition zone between the Alps, Dinarides and Pannonian Basin, characterized by a complex deformation pattern, highly variable crustal thickness, and moderate seismic hazard, supporting the development of the 2021 seismic hazard model of Slovenia. The hazard model was based on three seismic source models: area source model, fault source model and smoothed seismicity (point) source model. We estimated the lower seismogenic depth using seismological and geological data and compared them. The seismological estimate was based on two regional earthquake catalogues prepared for this study. In the area source model, estimates of lower seismogenic depth from seismological data are deeper or equal to the ones derived from geological data, except in one case. In the fault source model, we analysed each fault individually and chose seismological lower depth estimates in 12 among 89 faults as more representative. The seismogenic thickness for each individual fault source was determined for seismic coupling determination. The seismic coupling was assessed by two approaches, i.e. we chose the most trusted value from the literature, and the value determined for each fault individually by using the approach based on the updated regional fault and earthquake data sets. The final estimate of seismic coupling ranges from 0.77 to 0.38. We compared the tectonic moment rate based on long-term slip rate using different values of seismic coupling with the seismic moment rate obtained from the earthquake catalogue. The analysis is done for the whole area, as well as for the individual area zones. The analysis of N–S components of estimated slip for the largest faults in the area of west Slovenia shows that the regional geological and geodetic shortening rates are comparable. The total activity rate of three global seismic source models is compared, which gives up to a 10 % difference. Our results contribute to a better understanding of the seismic activity in the region. The presented approach for seismic coupling estimation can be applied in cases where the total slip rate is given instead of its seismic part and can be used at regional or national level. The approach is also suitable for the cross-border harmonization of the European seismic hazard modelling data.
Ključne besede: seismic hazard, modeling, Slovenia
Objavljeno v DiRROS: 18.03.2024; Ogledov: 110; Prenosov: 63
.pdf Celotno besedilo (11,29 MB)
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Comparison of elemental composition of surface and subsurface soils on national level and identification of potential natural and anthropogenic processes influencing its composition
Emil Pučko, Gorazd Žibret, Klemen Teran, 2024, izvirni znanstveni članek

Povzetek: The elemental composition of soils is governed by geogenic processes and anthropogenic activities. A comprehensive soil study was conducted on a national level, in which the elemental composition of soils from two different layers was compared with the intention to differentiate between natural and anthropogenic sources of elemental enrichments. Topsoil (0–5 cm) and subsoil (20–30 cm) samples were collected from 249 different locations on a national scale (Slovenia). Elemental composition for 55 major, minor, and trace elements (ICP-MS, aqua regia digestion) was determined on the fraction <0.063 mm. By calculating the enrichment ratios in different lithological units, it was determined that levels of Ti are higher in soils overlying metamorphic and igneous rocks, Zr and Ca are more abundant over carbonates, while levels of Ni are higher in soils overlying marlstones. Elevated levels of Hg were detected in subsoils in the historical Hg mining area in Idrija, which indicates the presence of nearby orebodies as a potential source for the geochemical anomaly. Spatial distribution of elements showed that higher levels of Pb, Zn, Cu, and Hg were detected in topsoils of urban areas, indicating that anthropogenic sources could be the potential cause of soil contamination. Pb, Zn, Cu, and Hg levels were up to four times higher in topsoils compared to subsoils sampled at historical mining areas (e.g., Mežica, Idrija, Litija), which shows that historical mining left a significant environmental impact. Although mining and smelting activities ended a few decades ago, soils in some areas are still heavily enriched with various metals. Some other potential anthropogenic sources of elements were identified, such as farming and ironworks. Based on the results of this study, we can conclude that by comparing elemental compositions of soils from different layers, we can recognise the origin of elemental enrichments.
Ključne besede: smelting, mining, urbanisation, traffic, ironworks, weathering
Objavljeno v DiRROS: 18.03.2024; Ogledov: 85; Prenosov: 33
.pdf Celotno besedilo (16,11 MB)

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, izvirni znanstveni članek

Povzetek: 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.
Ključne besede: moss, biomonitoring, air pollution, potentially toxic elements, Macedonia
Objavljeno v DiRROS: 06.02.2024; Ogledov: 156; Prenosov: 48
.pdf Celotno besedilo (9,82 MB)

Secondary deposits as a potential REEs source in South-Eastern Europe
Robert Šajn, Jasminka Alijagić, Ivica Ristović, 2024, izvirni znanstveni članek

Povzetek: 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.
Ključne besede: secondary raw materials, ESEE, rare elements, economic prospective
Objavljeno v DiRROS: 06.02.2024; Ogledov: 140; Prenosov: 37
.pdf Celotno besedilo (12,40 MB)

Hydrogeological characterization of karst springs of the white (Proteus anguinus anguinus) and black olm (Proteus anguinus parkelj) habitat in Bela krajina (SE Slovenia)
Katja Koren, Rok Brajkovič, 2023, izvirni znanstveni članek

Povzetek: The springs west of Črnomelj, in SE Slovenia, are the habitat of the black (Proteus anguinus parkelj) and the white olm (Proteus anguinus anguinus). Some of these springs are also the only known habitat in the world of endemic species of black olm. A steady decline in olm populations has been observed in this area over the past decades. Owing to the rapid runoff and groundwater flow high-resolution monitoring is essential in providing better insight into the hydrogeological characterization of the catchment area of springs. Specific factors and critical parameters of water behind said olm degradation have not yet been defined. Because the olm’s environment is largely aquatic, one potential critical parameter could be the higher water temperatures (>12 °C) or higher nitrate concentration (>9.2mg/l). The six-month observation of the springs (July – December 2021) point to water temperature as a potential critical parameter since the water temperature of the springs exceeded 12 °C in months July and August. Nitrate concentrations could also be a second critical parameter in the degradation of the olm’s habitat. Maximum nitrate concentrations above 9.2mg/l throughout much of the observation period (except for Dobličica spring). Due to less agricultural activity in December in the spring catchment area and a higher dilution rate due to reduced evapotranspiration and increased effective precipitation during this time of the year, the nitrate concentrations are decreased. The results of the measured parameters of groundwater could show the hydrogeological connection between the Otovski and Pački breg springs and between Šotor, Jamnice and Dobličica. The Obršec spring has an independent catchment area. A detailed estimation of the springs catchment area is possible due to a detailed geologic map. It is necessary to determine the origin of the nitrate (nitrate isotope analysis), to quantify the threshold values of the critical parameters, to define precisely all the causes of the olm deterioration, and to make proposals for appropriate measures to limit or even stop the decline of the olm population.
Ključne besede: hydrogeology, olm, ecology, nitrate, monitoring
Objavljeno v DiRROS: 16.01.2024; Ogledov: 151; Prenosov: 55
.pdf Celotno besedilo (13,65 MB)

Impact assessment of the Gajke and Brstje landfills on groundwater status using stable and radioactive isotopes
Sonja Cerar, Luka Serianz, Polona Vreča, Marko Štrok, Tjaša Kanduč, 2023, izvirni znanstveni članek

Povzetek: Waste disposal in landfills represents a severe threat to aquatic environments on the local, regional, and global levels. In Slovenia, there are 69 registered landfills where groundwater is regularly monitored. However, isotope techniques are not regularly employed. Therefore, we employed isotope analysis of hydrogen, carbon, and oxygen in combination with total alkalinity to assess the impact of the selected landfill on groundwater and to evaluate the biogeochemical processes at work. The δ18O, δ2H, δ13CDIC, 3H activity and total alkalinity were determined in October 2020 at 12 sampling points from the surrounding area of the Gajke and Brstje landfills and leachate from the Gajke landfill. The δ18O (-9.24 ± 0.3 ‰) and δ2H (-64.9 ± 2.7 ‰) in groundwater indicate that the main water source consists in direct infiltration of precipitation, with no significant isotopic fractionation. Total alkalinity in the investigated area ranges from 5.45 to 73 mM and δ13CDIC from –14.9 to +6.1 ‰, respectively. Higher values of total alkalinity (up to 73 mM), δ13CDIC (up to +6.1 ‰), δ18O (-7.64 ‰) and 3H (209.8 TU) are detected in the leachate, indicating biogeochemical process related to CO2 reduction or methanogenesis. Methanogenesis could be present at locations GAP-10/13 (Brstje landfill) and G-2 (Gajke landfill) with δ13CDIC values ranging from –8.2 to –7.6 ‰ and with dissolved oxygen values around 0 % and elevated 3H values (from 16 to 18 TU). This study demonstrates the effectiveness of isotopic analysis as a valuable tool for monitoring landfills, revealing shifts in biogeochemical processes within the groundwater there.
Ključne besede: groundwater, monitoring, landfill, stable isotopes, tritium, Gajke, Brstje
Objavljeno v DiRROS: 16.01.2024; Ogledov: 168; Prenosov: 60
.pdf Celotno besedilo (8,52 MB)

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