Application and improvement of soil spatial distribution mapping using advanced modelling techniques

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.</p

SPATIAL DISTRIBUTION OF CHEMICAL ELEMENTS IN SOILS FROM THE SOUTHEASTERN PART OF NORTH MACEDONIA (GEVGELIJA, VALANDOVO, BOGDANCI AND DOJRAN MUNICIPALITIES)

In this work, the contents and spatial distributions of 18 elements (Ag, Al, Ba, Ca, Cr, Cu, Fe, K, Li, Mg, Mn, Na, Ni, P, Pb, Sr, V, Zn) in the soils of the southeastern part of North Macedonia (Gevgelija–Valandovo–Bogdanci–Dojran region) are presented. For this purpose, a total of 86 soil samples were collected from 43 locations (43 samples of topsoil and 43 samples of subsoil). All samples were analyzsed by inductively coupled plasma with 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 (Fe, V, Mn, Cu, Ni, Zn, and Pb), Factor 2 (Ba, Li, and K), and Factor 3 (Mg, Al, Ca, and Sr). From the obtained data and the maps of spatial distribution, it could be concluded that the occurrence of the analyzed elements is related to the lithology of the region. Namely, it was found that the content of elements of Factor 1 is higher in soils dominated by Mesozoic volcanic rocks, Quaternary alluvial sediments, and Proterozoic gneisses and Paleozoic shales; the content of elements of Factor 2 is higher in soils in the north (where Mesozoic felsic plutonites dominate) and east (where Proterozoic gneisses and Paleozoic shales dominate) of the study area; and that elements of Factor 3 are present in soils from the area dominated by Quaternary alluvial sediments, Paleozoic carbonates and shales, and Mesozoic mafic plutonites. The only exception is the fact that the P content in the topsoil from the Gevgelija and Valandovo valleys along the Vardar and Anska rivers is higher than in the subsoil samples, which is probably due to the use of phosphate artificial fertilisers in agriculture

Spatial distribution of chemical elements in soils in the Polog region, Republic of Macedonia

The purpose of this study was to determine the presence and spatial distribution of various chemical elements in soil in the Polog region, Republic of Macedonia. For this purpose, geochemical monitoring techniques were applied for determination of 19 macro and trace elements (Al, B, Ba, Ca, Cd, Cr, Cu, Fe, K, Li, Mg, Mn, Na, Ni, P, Pb, Sr, V and Zn). A total of 116 soil samples (58 samples of topsoil and 58 samples of subsoil) were taken from predetermined referent locations. The collected samples were analyzed by the application of atomic emission spectrometry with inductively coupled plasma (ICP-AES). From the analyzed soil samples, 4 chemical associations were determined, from which three factors with lithogenic source (F1, F2 and F4) and one factor with mixed lithogenic and anthropogenic origin (F3). In factor 3 the anthropogenic impact is due to increased deposits of potassium in the surface soil layers in the southern parts of the Polog valley, where potassium fertilizers are used in agriculture. The elements which are included in the lithogenic factors are present in soil as a result of the geological structures in area where these elements are present (schists, carbonates, sandstones and sediments)

DISTRIBUTION OF CHEMICAL ELEMENTS IN SEDIMENTS AND ALLUVIUM SOILS FROM THE PČINJA RIVER BASIN, NORTH MACEDONIA

In this work, the distribution of chemical elements in sediment and alluvial soil samples from the Pčinja river basin was investigated. For this purpose, samples of sediments and natural and anthropogenic alluvium soils from the river and lake plains were collected along the course of the Pčinja river in the period from June to July 2017, according to a previously established sampling network with 10 sites on the rivers and 4 sites on the Glažnja and Lipkovo lakes. In addition to five sites on the Pčinja river, two samples were collected from the river of Tabanovska and one sample from the each tributaries of Kumanovsk, Konjarska and Kriva rivers. At each site, the following samples were collected: river sediment, lake sediment and natural alluvium (topsoil sample, 0–5 cm, and subsoil sample, 20–30 cm). In all samples collected, 22 macro- and trace elements (Аg, Al, As, Ba, Ca, Cd, Co, Cr, Cu, Fe, K, Li, Mg, Mn, Mo, Na, P, Ni, Pb, Sr, V and Zn) were analyzed by inductively coupled plasma – atomic emission spectrometry (ICP-AES). The contents of almost all the analyzed elements are within the expected values and are consistent with the lithology of the area studied. A multivariate factor analysis was applied to analyze the relationships between the number of variables. The method includes processing information from a large number of original variables and processing them into a smaller set (factor) with minimal loss of information from the original variables. From the obtained results, spatial distribution maps of the factors for each group and distribution maps the analyzed elements were created. It was found that the distribution of most elements follows the lithology of the study area, with the exception of some elements (As, Cu, P) whose increased contents are to urban, industrial and agricultural activities

ENRICHMENT OF SOME POTENTIALLY TOXIC ELEMENTS IN SOILS AFFECTED BY Pb-Zn MINING AND METALLURGICAL PROCESSING IN THE MITROVICA REGION, KOSOVO

The results of a study on the presence and enrichment of potentially toxic elements in surface soil in the Mitrovica region, Kosovo, are reported. The investigated region (301.5 km2) was covered by a sampling grid of 1.4×1.4 km and a total of 156 soil samples were collected. Inductively coupled plasma - mass spectrometry (ICP-MS) was applied for the determination of anthropogenic association of 12 elements: Ag, As, Au, Bi, Cd, Cu, Hg, Pb, Mo, Sb, Tl and Zn. For data evaluation, parametric and non-parametric statistics methods were used. Soil contamination is assessed on the basis of enrichment factor (EF). The average content of Pb was 19.6-fold; Cd 11-fold; Hg 5-fold; Zn 4.5-fold; As 4.3-fold; Sb 3.8-fold; Cu 3.2-fold and Ag 1.6-fold higher that European average values. Increased levels of the content of these metals showed that mining and smelter processing activities strongly affected in soils of the towns of Zveçan and Mitrovica and their environs. In the close vicinity of the cities of Zveçan and Mitrovica, the contents of the As, Cd, Cu, Pb and Zn were even higher than the corresponding intervention values according to the New Dutch list and were exceed in 122 km2 of the investigated area. Key words: soil pollution; potentially toxic elements; Mitrovica; Republic of Kosov

Distribution of lead and zinc in soil over the Bitola region, Republic of Macedonia

Data for the distribution of lead and zinc in topsoil and subsoil over the Bitola region, Republic of Macedonia, known for its coal mine and thermoelectric power plant are presented. The study area (1400 km2) is covered by a sampling grid of 5×5 km with a total of 58 spots. The samples were collected at two depths: topsoil (0–5 cm) and subsoil (20–30 cm). The samples were analyzed by inductively coupled plasma-atomic emission spectrometry (ICP-AES). The obtained results of these two elements were statistically processed and maps of areal distribution were prepared. It was assumed that the higher contents of Pb and Zn are connected with the anthropogenic influence by the fly ash from the thermoelectric power plant deposed on the open as well as the influence of the high frequency traffic near the city of Bitola.Key words soil; lead; zinc; Bitola; Republic of Macedonia

Geological characteristics of the Republic of North Macedonia

Detailed description of the geological characteristics of the Republic of North Macedonia is given. The characteristics of the six major tectonic units are described: the Vardar zone (VZ) in Central Region, the Pelagonian massif (PM), the West-Macedonian zone (WMZ) and a small part of the Cukali-Krasta zone (CKZ) in the west, and the Serbo-Macedonian massif (SMM) and the Kraishtide zone (KZ) in the east. The geological map with these units is also shown, including the most presented lithological units: Quaternary alluvial and deluvial/proluvial sediments, Neogene, Paleogene and Mesozoic clastic rocks, Mesozoic, Paleozoic and Proterozoic carbonate rocks, Paleozoic and Proterozoic metamorphic rocks from Pelagonian and Serbo-Macedonian massif and Neogene, Paleogene, Mesozoic and Paleozoic magmatic rocks. Additionally, special attention is given to the Neogene and the Quaternary in North Macedonia

Spatial distribution of heavy metals in soils in the Republic of Macedonia

The distribution of various elements in soils in the Republic of Macedonia was analyzed in termsof air pollution with heavy metals carried out for more than 10 years within the European moss biomonitoring programmeof air pollution in Europe. In 2010 in parallel to moss sampling, on the same locations, soil samples were alsocollected using a network of 72 locations all over the country. In total of 144 samples (top and bottom soil) werecollected and 18 elements (Al, Ba, Ca, Cr, Cu, Fe, Ga, K, Li, Mg, Mn, Na, Ni, P, Pb, Sr, V and Zn) were analyzed usinginductively coupled plasma – atomic emission spectrometry (ICP-AES). Both, top and bottom soil samples wereanalyzed to identify possible anthropogenic influences and to assess whether the metal content is associated with anthropogenicsources or it is a result of lithology. The obtained data were statistically processed and distribution mapsfor all analyzed elements were prepared. The results are compared with international standards for soil and with thelocations of the industry. The analysis generally indicates a connection with the lithological appearances, but alsoshows a possible association with certain industrial activities

DISTRIBUTION OF CHEMICAL ELEMENTS IN SOIL SAMPLES FROM PELAGONIA REGION, REPUBLIC OF MACEDONIA

The aim of this study is to establish a global geochemical reference baseline by presenting the results of a first systematic investigation of spatial distribution of different chemical elements in soil over of the Pelagonia region, Republic of Macedonia. For this purpose, 228 soil samples (from 131 locations) were analyzed to determine the content of 17 major and trace elements in the soil from this region and to assess the size of the area eventually affected by heavy metals pollution. All samples were analyzed by atomic emission spectroscopy with inductively coupled plasma (ICP-AES). Factor analysis with multivariance R-method is applied in order to show the associations of chemical elements. Three factors were obtained. Factor 1 (Al, Ba, Mg, Mn, Fe, Ni, P and V), Facror 2 (Cr, Cu, Pb and Zn) and Factor 3 (Ca and Sr). It was established that the distribution of these associations are mostly as a result of the complex geology and lithology of the region.</p

Variability assessment of metals distributions due to anthropogenic and geogenic impact in the lead-zinc mine and flotation „Zletovo” environs (moss biomonitoring)

Moss species (Hypnum cupressiforme, Scleropodium purum and Campthotecium lutescens) wereused as suitable sampling media for biomonitoring the origin of heavy metal pollution in the lead–zinc mine and flotationenviron near the town of Probištip. The 21 metals contents were determined by atomic emission spectrometrywith inductively coupled plasma (ICP–AES). Data processing was applied with combinations of multivariate statisticalmethods: factor analysis, principal component analysis and cluster analysis. The main anthropogenic markersin the investigated area were Pb and Zn (maximal values of 200 and 186 mg kg–1, respectively). The factor analysissingled out (in the increasing scale) the following associations: F1/D1: Fe &lt; Mo &lt; Pb &lt; Na &lt; Cd &lt; Mg &lt; Zn &lt; Ag &lt;Cu and F2/D2: Mn &lt; Ni &lt; K &lt; P &lt; Ba &lt; Sr &lt; Ca &lt; As &lt; Cr &lt; Al &lt; V &lt; Li. The anthropogenic elements contents varyindependent from the moss species, but depending on the distancing from the pollution source, there are positive correlation.Long distance distribution from the emission source doesn’t occur