This paper provides an overview of the physical and chemical landscape changes that have occurred at four reference sites due to historical mining and smelting activities within Slovenia, and their ...comparison with similar sites around the World. Literature review has been made with the intention to identify major pollutant sources, its dispersion control factors, and effects. The four reference sites are Idrija, with more than 500‐year Hg mining and ore smelting history, the Meža Valley, also with a 500‐year PbZn mining and smelting history, the Celje area where Zn was smelted for 100 years and the Drava River alluvial plain, which is contaminated because of historical PbZn mining upstream. Based on the comparison between the four abovementioned reference sites and similar sites around the world that are situated in different landscapes and climates, we identified major sources of contamination, which are the erosion of mine and ore processing wastes, and atmospheric emissions of metal‐containing particles from smelters. In the first case, major control factors are rainfall pattern and river gradient, controlling erosion and sediment deposition patterns. In the second case, the prevailing control factors are topography and the dominant wind directions.
The results of a study on the spatial distribution of different elements in surface soil (0–5cm) in the former Pb―Zn mining Kosovska Mitrovica/Mitrovicë region, in Kosovo are reported. It proved very ...difficult to organise this geochemical investigation, because of the complex political situation and issues related to the two main ethnic groups. The investigated area (301.5km2) was covered by a sampling grid of 1.4×1.4km. Soil samples were collected from 156 sampling sites. Inductively coupled plasma-mass spectrometry (ICP-MS) was used to determine 36 elements (Ag, Al, As, Au, B, Ba, Bi, Ca, Cd, Co, Cr, Cu, Fe, Ga, Hg, K, La, Mg, Mn, Mo, Na, Ni, P, Pb, S, Sb, Sc, Se, Sr, Th, Ti, Tl, U, V, W and Zn). Parametric and non-parametric statistical methods were used to evaluate the data, and factor analysis was employed to reduce the number of variables to five factors. The data were interpolated by using a GIS universal kriging technique; maps for particular elements, as well as for factor score values in topsoil, were constructed. Elements such as Ag, Pb, Sb, Bi, Zn, Cd, As, Cu, Hg, Au, Tl and Mo in soil samples appeared as an anthropogenic association due to the Pb―Zn ore mining and processing activities. In the investigated area, the average content of Pb in soil is 20-fold higher than the European median; Cd 11-fold, Hg 5.5-fold, As 4.6-fold, Zn 4.2 and Cu 3.2-fold higher. In the narrower vicinity of K. Mitrovica/Mitrovicë and Zvečan/Zveçan, the content of the aforementioned elements is even higher than the intervention values, according to the New Dutch list, and were exceeded in 152km2 of the investigated area.
•The spatial distribution of elements in soil at former Pb―Zn mines and smelter.•ICP-MS was applied for the determination of 36 elements.•With FA, one anthropogenic and four geogenic associations have been isolated.•The data were interpolated by using a GIS universal kriging technique.•The intervention values of Pb, Zn, As, Hg, and Cu are exceeded in 152km2.
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.
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.
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.
The main purpose of this contribution is to develop realistic prediction digital soil maps in order to increase their visuality, and to evaluate and compare the performance of different modeling ...techniques: a) Kriging, b) Artificial Neural Network - Multilayer Perceptron (ANN-MLP) and c) Multiple Polynomial Regressions (MPR). The following criteria were used to determine selection of the testing site for the modeling: (1) intensive metal ore mining and metallurgical processing; (2) geomorphological natural features; (3) regular geological setting, and (4) the remaining minefields. The success of Digital Soil Mapping and the plausibility of prediction maps increases with the availability of spatial data, the availability of computing power for processing data, the development of data-mining tools, geographical information systems (GIS) and numerous applications beyond geostatistics. Advanced prediction modeling techniques, ANN-MLP and MPR include geospatial parameters sourced from Digital Elevation Models (DEM), land use and remote sensing, applied in combination with costly and time-consuming soil measurements, developed and finally incorporated into the models of spatial distribution in the form of 2D or 3D maps. Innovative approaches to modeling assist us in the reconstruction of different processes that impact the entire study area, simultaneously. This holistic approach represents a novelty in contamination mapping and develops prediction models to help in the reconstruction of main distribution pathways, to assess the real size of the affected area as well as improving the data interpretation.
The objectives of this study are as follows: (a) an assessment of the geochemical background signature of the Drava Valley before the industrial revolution; (b) an evaluation of anthropogenic ...geochemical influences on the alluvial plains and river terraces in the valley; and (c) a determination of the spatial distribution of trace elements in the alluvial soils of the Drava River downstream of the Austrian–Slovenian border to the confluence of Mura and Drava Rivers.
Samples of topsoil (depth of 0–5
cm) and subsoil (depth of 20–30
cm) were collected from 134 sampling sites on alluvial plains and river terraces. Analysis for 41 chemical elements was performed. Based on a comparison of statistical parameters, the spatial distribution of particular elements and the results of factor analysis, one anthropogenic and three natural geochemical associations were identified. The anthropogenic association (As–Ba–Cd–Mo–Pb–Sb–Zn) is mostly a result of historical zinc and lead mining and smelting in the Drava River watershed. The natural geochemical associations (Al–Fe–K–Co–Cr–Cu–Li–Ni–Rb–Sc–Th, Ti–Ce–La–Nb–Ta and Ca–Mg–Sr) were mainly influenced by lithology. The entire assessed area of about 130
km
2 is, according to Slovenian and Croatian legislation, critically polluted with trace elements, especially zinc.
► Mines and smelters contributed to the Drava alluvial sediments. ► One anthropogenic and three natural geochemical associations were identified. ► Al–Fe–K–Co–Cr–Cu–Li–Ni–Rb–Sc–Th, Ti–Ce–La–Nb–Ta and Ca–Mg–Sr are effects of lithology. ► As–Ba–Cd–Mo–Pb–Sb–Zn is influenced by historical zinc and lead mining and smelting.
The objective of this work is to study the distribution of chemical elements in topsoil and subsoil, focusing on the identification of anthropogenic (human-made) and geogenic (natural) element ...sources in a former metallurgical industrial area. Samples of topsoil (0–5
cm depth) and subsoil (20–30
cm depth) were collected from 60 different sites in a 52
km
2 area around the town of Zenica, Bosnia and Herzegovina. The study was based on comparisons of statistical parameters, spatial distribution of selected elements, and the results of cluster and factor analyses. Two natural geochemical associations and one anthropogenic association were identified. The natural geochemical associations (Al, Ce, K, La, Li, Nb, Rb, Sc, Ta, Ti Th, V, and Y and Co, Cr, Na, Ni, and Mg) are predominantly influenced by lithological factors, whereas the anthropogenic association (Ag, Bi, Cd, Cu, Hg, Mo, Pb, Sb, and Zn) is the result of past iron metallurgy in the study area. Although Zenica was the largest ironwork in former Yugoslavia, the observed level of contamination is rather low when compared to the iron and steel industry in Bosnia, Herzegovina and Slovenia.
► Identification of anthropogenic and geogenic sources in former industrial area. ► Two natural and one anthropogenic geochemical association were identified. ► High concentrations of Co, Cr, and Ni as a result of rock weathering. ► Ironworks, coal mining,traffic and other actions caused high level of trace elements. ► A comparison of concentrations of several trace elements from Slovenia and B&H.
The main objective of this paper is to compare and improve spatial distributions models for Pb and Cu in air and soil using the universal kriging and ANN-MLP at the macro regional scale. For this ...purpose, both models have been applied for visualization of a spatial distribution of lead (Pb) and copper (Cu) in a morphologically and geologically complex area. Two river basins in the eastern part of North Macedonia, have been selected as the main research region due to the extensive anthropogenic impact of long-lasting mining activities, with emphasis on the specific geochemistry of the area. Two environmental media (soil and moss) have been selected as they are much more available as space from biospheres submitted for destruction processes globally. Surface soil and moss as bio-indicator element measurements were submitted in correlation with geospatial data obtained from DEM, land cover data, and remote sensing, and are incorporated into spatial distribution mapping using an advanced prediction modeling technique, ANN-MPL. Both methods have been further compared and evaluated. The comparative data outputs have led to the general conclusion that ANN-MPL gives more realistic, reliable, and comprehensive results than the universal kriging method for the reconstruction of main distribution pathways. The more the factors influencing the process of distribution of the elements increase, the more the use of ANN-MPL improves.
This study has the purpose of developing a realistic soil prediction maps of the spatial distribution of elements by evaluating and comparing different modelling techniques: Kriging, artificial ...neural network-multilayer perceptron (ANN-MLP) and multiple polynomial regressions (MPR). The Stavnja Valley was selected as a test area due to the following reasons: (1) intensive metal ore mining and metallurgical processing; (2) peculiar geomorphological natural features; (3) regular geological setting, and (4) the remaining minefields. Geospatial parameters from digital elevation models (DEM) are used as an input to advanced prediction modelling techniques: ANN-MLP and MPR. Soil measurements, land use data, and remote sensing are applied, developed, and finally incorporated into the models of spatial distribution in the form of 2D or 3D maps. In order to reconstruct the different processes that influenced the entire study area simultaneously, we used novel approaches to modelling. This comprehensive approach not only represents an innovation in contamination mapping, but developed prediction models also help in the reconstruction of main distribution pathways, assess the real size of the affected area, and improve the data interpretation.
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