Assessment of radiological hazards of soils from the city of Bitola (Macedonia) and its environs.

To establish the radioactivity level of soils and assess the associated radiological impact on residents, 58 samples from the town of Bitola and its environs were collected. After conducting gross alpha and gross beta measurements with a gas-flow proportional counter as a preliminary screening test, subsequent gamma-spectrometry measurements reveal the presence of 40K, 226Ra, 232Th, and 137Cs in the soil samples as radionuclides with the highest impact. The absorbed gamma dose rate, the annual effective dose, radium equivalent activity, external hazard index, gamma index, excess lifetime cancer risk, and annual gonadal dose were calculated using the obtained activity concentrations of the radionuclides. Upon comparison with similar studies conducted in the Balkan countries, the obtained results for radiation hazard indices were found to be the highest in the region. Coloured maps were generated to visually represent the spatial distribution of the absorbed gamma dose rate in air and annual effective dose, clearly indicating the combined influence of geology and human activities, including the nearby thermoelectric power plant operation.

Distribution of some natural and artificial radionuclides in soil from the city of Bitola (Macedonia) and its environs.

The aim of the study is a thorough investigation of the radioactivity level in soils of the town of Bitola (Macedonia) and its environs. Topsoil samples collected from 58 locations within a 5 × 5 km grid were analysed. Serving as a screening, gross alpha and beta activity measurements were performed using gas-flow proportional counter. Gamma-spectrometric measurements revealed the presence of three natural (40K, 226Ra, 232Th) and one artificial radionuclide (137Cs) in the samples. The activity concentrations of these radionuclides were consistent with the results of similar studies in neighbouring areas. Spatial distribution maps and factor analyses have revealed that the activity concentrations of the natural radionuclides are strongly influenced by geology and have no significant influence from human activities. A correlation of 137Cs activity concentrations with terrain elevation was also observed. The aim of the study is a thorough investigation of the radioactivity level in soils of the town of Bitola (Macedonia) and its environs. Topsoil samples collected from 58 locations within a 5 × 5 km grid were analysed. Serving as a screening, gross alpha and beta activity measurements were performed using gas-flow proportional counter. Gamma-spectrometric measurements revealed the presence of three natural (40K, 226Ra, 232Th) and one artificial radionuclide (137Cs) in the samples. The activity concentrations of these radionuclides were consistent with the results of similar studies in neighbouring areas. Spatial distribution maps and factor analyses have revealed that the activity concentrations of the natural radionuclides are strongly influenced by geology and have no significant influence from human activities. A correlation of 137Cs activity concentrations with terrain elevation was also observed.

Mercury distribution and contamination in the soils of the Mitrovica region, Republic of Kosovo.

The study was carried out to define the distribution of mercury in surface soils in the Mitrovica region, Republic of Kosovo and to assess the level and extent of contamination. A total of 156 soil samples were collected from a depth of 5 cm at each grid point of 1.4 × 1.4 km in an area of 301.5 km2. The mercury content was found to be between 0.02 mg/kg and 11.16 mg/kg. The average Hg content (0.49 mg/kg) exceeded the mean content in European (0.037 mg/kg) and world (0.06 mg/kg) soils by 13.2 and 8.2 times, respectively. From the calculated enrichment factors (EF) and the geo-accumulation index (I-geo), as well as from the distribution map of Hg content, it is evident that the soils of the study area are highly contaminated with mercury, with extremely high enrichment of Hg in the soils of Zone I, which was classified as the most contaminated zone with Hg and other potentially toxic elements in the study area as well as in the towns of Zveçan and Mitrovica. The higher Hg content is of anthropogenic origin, mainly due to lead and zinc mining and metallurgical activities in the study area. The mercury levels were also found to exceed the New Dutch List target value (0.3 mg/kg) in 90 km2 of the study area.

Lithological distribution of rare earth elements in soils in the As-Sb-Tl Allchar mining area, North Macedonia.

Despite the growing interest, the information available on rare earth elements (REEs) in the last two decades is relatively premature and sparse. The importance of these elements as indicators of soil and physiological processes and responses have contributed to the increased interest in these previously less considered elements in the environmental sciences. This study provides an overview of the content and distribution of rare earth elements in the soil in the vicinity of the hydrothermal volcanogenic As-Sb-Tl deposit of Allchar, North Macedonia. Elemental contents were determined by inductively coupled plasma mass spectrometry (ICP-MS). The light rare earth elements (LREEs) content in the study area ranges from 8.92 to 188 mg/kg, while the heavy rare earth elements (HREEs) content ranges from 1.95 to 42.7 mg/kg. It can be concluded that there is some enrichment of light REEs in the volcanic intrusive rocks of the Allchar mine area, including latite, quartz-latite, trachyte and occasionally andesite and dacite. The spatial distribution of HREEs is closely related to the lithology of the region, especially the sandstone and claystone, followed by layered and massive carbonate rocks (limestone, dolomite, marble) that occurred in the Middle and Upper Triassic.

Levels and distribution of chemical elements in house dust from the area of an abandoned Pb-Zn smelter in North Macedonia.

The content of 41 chemical elements (Ag, Al, As, Au, Ba, Br, Ca, Cd, Ce, Co, Cr, Cs, Cu, Fe, Hf, In, K, La, Li, Mg, Mn, Mo, Na, Nd, Ni, P, Pb, Rb, Sb, Sc, Se, Sm, Sr, Tb, Th, Ti, Tm, U, V, W, and Zn) was determined in attic dust, household dust and soil samples collected from 33 houses in the area of the town of Veles, North Macedonia. Silver, Cd, Cu, Li, P, and, Pb were analyzed by inductively coupled plasma - atomic emission spectrometry while the other elements were analyzed by neutron activation analysis. The study area has been continuously exposed to high amounts of potentially toxic elements due to the emission from an abandoned Pb-Zn smelter plant. In this study, attic and household dust together with soil samples collected from the yards of the houses were used to assess the level of historical and present air contamination by potentially toxic elements. It was found that the contents of Ag, As, Cd, Cu, In, Pb, Sb, Se, and, Zn in dust samples represented an anthropogenic association of elements, with very high contents in samples collected from the town of Veles, which is close to the Pb-Zn smelter, compared with those collected from the mountainous area.

Regional air quality study by assessing trace metal atmospheric deposition.

This study addresses the atmospheric deposition of trace elements investigated in Albania, Croatia and Macedonia in 2010 as part of the European Moss Study. This study provides data on the concentration of ten metals (Cd, Cr, Cu, Ni, Pb, V, Zn, Fe, Al, and Li) in naturally growing mosses. In general, all concentration data follow a lognormal distribution. Cd, Cr, Ni, and Zn show strong fluctuations in the moss samples from Albania and Macedonia, and Pb, Fe, and Al in the mosses from Croatia. The concentrations of Cd, Cu, and Zn were higher in the samples from Croatia than in those from Albania and Macedonia; the concentrations of Cr, Ni, V, Fe, Al, and Li were higher in the samples from Albania than in those from Croatia and Macedonia; and a higher concentration of Pb was found in the samples from Macedonia. The observed relationship between the concentration of lithogenic elements (Al, Fe, and V) and the air quality index (AQI) confirms that moss species have a high capacity to retain atmospheric deposition particles. The anthropogenic emission sources of these elements from local and long-range transport were considered to be the most important factors affecting air quality in the studied areas.

Distribution and statistical analysis of major and trace elements in the bee pollen from the territory of Republic of Kosovo.

The objective of this study was the determination of major and trace elements in the bee pollen samples from the whole territory of Republic of Kosovo. Pollen, as a natural plant product, is exposed to different contaminations absorbed by plants from the soil through the root system or with water intake, as well as to pollutants of different origins, including anthropogenic ones, deposited directly on pollen. In total 67 pollen samples were collected in 2019. The samples were analyzed for 27 macro and microelements by using ICP-AES and ICP-MS. The mean content of major elements in bee pollen was 4065, 3455, 1375 and 549 mg/kg for K, P, Ca and Mg, respectively. The range of the contents for some potentially toxic elements was 11.9-139.1, 1.9-16, 0.11-6.25, 0.01-0.329 and 0.001-0.38 mg/kg for Zn, Cu, Pb, Cd and As, respectively. Three groups of elements of mixed origin were identified through factor analysis: the first and the third Factors, are mostly of geogenic origin (Ag, Li, Al, Fe, Ca, Sr, K, Mg and P and Co, Ni, Cr, Cu and Mn) and the second Factor association is related to anthropogenic processes (Sb, As, Pb, Tl, Sn and Cd).

Biomonitoring and assessment of toxic element contamination in floodplain sediments and soils using fluorescein diacetate (FDA) enzymatic activity measurements: evaluation of possibilities and limitations through the case study of the Drava River floodplain.

The EU Water Framework Directive requires the monitoring and evaluation of surface water sediment quality based on the assessment of risk posed by contamination on the biotic receptors. Floodplain sediments are important receptors of potentially toxic element (PTE) contamination from the upstream catchment areas, and floodplains host climate-sensitive riverine ecosystems and fertile agricultural areas at the same time. This study investigates the effect of PTE contamination on microbial communities in floodplain sediments and soils using the fast, inexpensive and reliable fluorescein diacetate (FDA) method in order to estimate its applicability for sediment quality monitoring and preliminary toxicity-based risk assessment. Sediment and soil samples were collected from the actively flooded alluvial plain and the river terrace areas along a 130-km stretch of the large Drava River floodplain known to be widely contaminated by historical mining, smelting and the associated industry in the upstream Alpine region. Results of detailed data analysis show that the total microbial activity represented by the measured FDA values is related to PTE (As, Cu, Zn, Cd, Pb) concentrations, but this relationship shows significant heterogeneity and depends on the spatial location and on the soil properties such as organic matter content, dissolved salt and nutrient content, and it is specific to the toxic elements. Results show that some microbe species appear to be able to adapt to the elevated PTE concentrations in toxic soil micro-environments, over time. Despite the observed heterogeneity of microbial activity, the results revealed a breakpoint in the FDA dataset around the FDA = 3 FC (fluorescein concentration) value suggesting that microbial activity is controlled by thresholds.

Moss biomonitoring of air pollution with potentially toxic elements in the Kumanovo Region, North Macedonia.

A study was carried out to investigate air deposition and to explore the natural distribution and contamination with potentially toxic elements (PTEs) in the Kumanovo Region, North Macedonia, by using moss samples as biomonitors for air pollution. The distribution of 51 elements was detected in 42 moss samples collected from this area. Moss samples were analyzed following microwave digestion by inductively coupled plasma-atomic emission spectrometry (ICP-AES) and inductively coupled plasma-mass spectrometry (ICP-MS). It was found that the atmospheric deposition for some PTEs in the moss samples in specific parts of the study area is influenced by anthropogenic and urban activities. R-mode factor analysis was used to identify and characterize element associations, and six associations of elements were determined. Four factors were separated from the group of macroelements determined by ICP-AES: Factor 1 (Al, Cr, Fe, Li, Ni, V, and Zn), F2 (K, Mg, and P), F3 (Ba and Sr), and F4 (Cd, Pb, and Zn); and two associations were separated from the group of trace elements determined by ICP-MS: Factor 1 (As, Co, Cs, Ga, Ge, Sc, Ti, Y, Zr, and rare earth elements-REEs) and Factor 2 (Bi, Br, Hg, I, Sb, Sn, and W).

Assessment of natural and anthropogenic factors on the distribution of chemical elements in soil from the Skopje region, North Macedonia.

The main objective of this study is to present the distribution of different chemical elements in soil samples from the Skopje region, North Macedonia. To determine the level of presence of chemical elements, soil samples are collected from a total of 60 locations. From each location, from an area of 5 × 5 km2 samples of soil are collected: topsoil (0-5 cm) and subsoil (20-30 cm). The soil samples were analyzed for 69 elements by using two instrumental methods: inductively coupled plasma-atomic emission spectrometry (ICP-AES) for macro-elements and inductively coupled plasma-mass spectrometry (ICP-MS) for trace elements. A factor analysis was applied to analyze the factors affecting the linear combination variables grouped at the same factor. Spatial distribution maps of each factor as well as distribution maps for the analyzed elements were prepared by universal kriging interpolation. It was found that the distribution of most elements follows the lithology of the examined area, except for some elements (Cd, Cu, Fe, Hg, Mn, Pb, and Zn) whose higher contents are found in the area of the city of Skopje as a result of urban and industrial activities (traffic, metal processing, fossil fuel combustion for heating).

Statistical analysis of atmospheric deposition of heavy metals in Kosovo using the terrestrial mosses method.

Heavy metals presence in the air in the territory of Kosovo was estimated using mosses as biomonitors. The periodic smog over the territory of Kosovo, particularly around industrial sites and cities, is a clear indication of air pollution which unavoidably will contain heavy metals, because of the nature of the industries in area. This work was carried out aming to assess the presence of heavy metals in the air, identify the most polluted sites, and the origins of pollution. Heavy metals such as Al, Cd, Cr, Cu, Fe, Ni, Pb, and Zn, were determined in 45 moss samples. Statistical analysis was performed to better explain the data. The most polluted sites appeared to be in Zveqan, Stanterg, Prapashticë, Siboc, and Lupç. The contamination factor (CF) showed that only Cu and Zn had no or almost no contamination levels over the range of moss samples with CF < 1, while Cd and Pb gave extremely high values, CF > 27. Pollution load index (PLI) also showed that only a few samples are moderately polluted 2 < PLI ≤ 3, while most of the samples appeared to be highly polluted 4 < PLI ≤ 5, and very highly polluted PLI > 5.

Occurrence and enrichment sources of cobalt, chromium, and nickel in soils of Mitrovica Region, Republic of Kosovo.

The main purpose of this study is to determine the differences between anthropogenic sources and lithogenic sources of the content of certain potentially toxic elements in the region of Mitrovica, Republic of Kosovo. For that purpose, the results of a study on the spatial distribution and enrichment of cobalt, chromium and nickel in surface soil from Mitrovica and its environ, are reported. The average content of Co, Cr and Ni in soil amounts to 22 mg kg-1, 60 mg kg-1 and 96 mg kg-1, respectively. Spatial distribution maps of Co, Cr and Ni shows their predominance in the area of Triassic serpentinites on the North-eastern and Western parts of study area. The lowest contents are found on the outcropping of Miocene latites, quartz-latites and pyroclastites. It has been established that the increased content of Co, Cr and Ni in soils from this area is of lithogenic origin. It is shown that content of Co, Cr and Ni exceeds the target Dutch value in 173 km2, 82 km2 and 256 km2 (from 302 km2 of the study area), respectively, while the content of Cr and Ni exceeds the action Dutch value in 17 km2 and 63 km2, respectively.

Searching for lichen indicator species: the application of self-organizing maps in air quality assessment-a case study from Balkan area (Serbia).

The subject of this paper is the possibility of using self-organizing map (SOM) in the biomonitoring studies. We used lichens as biomonitors to indicate different degrees of air quality. This research included all of 88 lichen species that was collected at 75 investigated points. These lichen species showed the different responses to air pollution. The air quality was assessed by IAP (index of atmospheric pollution) values. The IAP values were calculated for all of investigated points on the territory of four natural and one urban ecosystem. Calculated IAP values were in range of 10 to 75. On the basis of the lichen data and IAP values, we have employed SOM analysis that distinguished three clusters (A, B, and C). It presented lichen indicator species for each cluster: 16 species for cluster A, 18 species for cluster B, and two species for cluster C. This paper presents a useful method to find indicator species.

Study of nitrogen pollution in the Republic of North Macedonia by moss biomonitoring and Kjeldahl method.

In the summer of 2005 and 2010, moss samples were collected from 72 sampling sites evenly distributed all over the territory of Republic of North Macedonia. Kjeldahl method was used to determine the nitrogen content in the samples. Descriptive statistics and distribution maps were prepared. Data obtained from these two surveys were compared, and additional comparison was done with data obtained from similar studies in the South-Eastern European countries and Finland as a clean area. The median value of N content in the samples collected in 2005 is 1.21%, varies from 0.70% to 1.54%, while the content of N in samples collected in 2010 ranges between 0.68% and 1.75% with the median value of 1.06%. High contents of N were found in the Northern and Central parts of the country mainly as a result of agricultural activities, industry and traffic.

Spatial distribution and pollution assessment of heavy metals in soil from the Republic of North Macedonia.

The purpose of the study was to determine the spatial distribution and pollution assessment of 39 chemical elements in soil from the Republic of North Macedonia. From the whole territory of the country top soil samples (0-30 cm) were collected from 995 locations with a grid of 5 × 5 km distance between the sampling locations. Two analytical techniques were used for the analysis of soil samples: inductively coupled plasma-atomic emission spectrometry and inductively coupled plasma-mass spectrometry. Based on a comparison of statistical parameters, spatial distribution of particular elements and results of cluster and factor analysis, four mаin geochemical associations were identified: (1) association connected with the Neogene and Quaternary volcanism (Ba, Be, Ce, Hf, K, La, Rb, Th, Tl, U and Zr); (2) association of siderophile elements (Co, Cu, Fe, Mn, Sc, Ti and V); (3) association connected with ophiolites and Mesozoic ultrabasic magmatic rocks of Vardar zone (Cr and Ni) and (4) chalcophile (sulphide) elements (As, Bi, Cd, Pb, Sb, Sn and Zn). The regional distribution was prepared according to the eight statistical regions in Macedonia, distribution according to 15 most common geological formation and distribution according to 13 pedological units.

Geochemical characteristics of soil of the city of Skopje, Republic of Macedonia.

This study represents the first systematic investigation of the spatial distribution of different chemical elements in the soil of the city of Skopje, Republic of Macedonia. For this purpose, surface soil samples from 234 locations were analyzed to determine the content of 20 major and trace elements (Ag, Al, As, Ba, Ca, Cd, Cr, Cu, Fe, K, Li, Mg, Mn, Na, Ni, P, Pb, Sr, V and Zn) to assess the size of the areas eventually affected by heavy metal pollution. All samples were analyzed by atomic emission spectroscopy with inductively coupled plasma (ICP-AES). Cluster and factor analysis (R-mode) were applied in order to show the associations of chemical elements. Four factors were obtained: Factor 1 (K, Na, Ba and Al), Factor 2 (Cr, Ni, Mg and Fe), Factor 3 (Zn, Cd and Cu) and Factor 4 (Sr and Ca). It was established that the distribution of the associations of F1, F2 and F4 are mostly as a result of the complex geology and lithology of the region while the association of F3 represents an anthropogenic association.

Enchasing anthropogenic element trackers for evidence of long-term atmospheric depositions in mine environs.

In this work attic dust was examined as historical archive of anthropogenic emissions, with the aim of elucidating the pathways of enrichments associated with exploitation of Cu, Pb, and Zn minerals in the Bregalnica river basin region. Attic dust samples were collected from 84 settlements. At each location for attic dust sampling, topsoil samples from the house yards were also collected. Mass spectrometry with inductively coupled plasma (ICP-MS) was applied as analytical technique for determination of Ag, Bi, Cd, Cu, In, Mn, Pb, Sb, Te, W, and Zn. The Universal Kriging method with linear variogram interpolation was applied for the construction of spatial distribution maps. Thеsе elements are normally associated with air pollution (Cd-Pb-Zn), and usually are not influenced by lithological background. This investigation fortifies an extended anthropogenic association (Ag, Bi, In, and Mn) that implement some other anthropogenic activities such as agricultural activities (use of urban sludge, manure and fertilizers) or their occurrence can be a secondary affection from mine poly-metallic pollution. Spatial patterns showed intensive deposition in the areas of Pb-Zn mining activities ("Sasa" and "Zletovo" mines) and copper mine "Bucim". Long-distance distributions of higher contents of these elements from the mines were not detected.

Geochemical properties of topsoil around the coal mine and thermoelectric power plant.

The results of the systematic study of the spatial distribution of trace metals in surface soil over the Bitola region, Republic of Macedonia, known for its coal mine and thermo-electrical power plant activities are reported. The investigated region (3200 km2) is covered by a sparse sampling grid of 5 × 5 km, but in the urban zone and around the thermoelectric power plant the sampling grid is denser (1 × 1 km). In total, 229 soil samples from 149 locations were collected including top-soil (0-5 cm) and bottom-soil samples (20-30 cm and 0-30 cm). Inductively coupled plasma - atomic emission spectrometry (ICP-AES) was applied for the determinations of 21 elements (Al, As, B, Ba, Ca, Cd, Co, Cr, Cu, Fe, K, Li, Mg, Mn, Na, Ni, P, Pb, Sr, V and Zn). Based on the results of factor analyses, three geogenic associations of elements have been defined: F1 (Fe, Ni, V, Co, Cr, Mn and Li), F2 (Zn, B, Cu, Cd, Na and K) and F3 (Ca, Sr, Mg, Ba and Al). Even typical trace metals such as As, Cd, Cu, Ni, P, Pb and Zn are not isolated into anthropogenic geochemical associations by multivariate statistical methods still show some trends of local anthropogenic enrichment. The distribution maps for each analyzed element is showing the higher content of these elements in soil samples collected around the thermoelectric power plants than their average content for the soil samples collected from the whole Bitola Region. It was found that this enrichment is a result of the pollution by fly ash from coal burning which deposited near the plant having a high content of these elements.

Quantitative assessment of metal elements using moss species as biomonitors in downwind area of lead-zinc mine.

Distributions of a total of 21 elements were monitored in significantly lead-zinc polluted area using moss species (Hypnum cupressiforme and Camptothecium lutescens) used interchangeably, covering a denser sampling network. Interspecies comparison was conducted using Box-Cox transformed values, due to their skewed distribution. The median concentrations of trace elements in the both mosses examined decreased in the following order: Fe>Mn>Zn>Pb>Cu>Ni∼Cr∼As>Co>Cd>Hg. For almost all analyzed elements, H. cupressiforme revealed higher bio-accumulative abilities. For arsenic contents was obtained ER-value in favor of C. lutescens. The ER for the element contents according to the distance from the pollution source in selected areas was significantly enriched for the anthropogenic introduced elements As, Cd, Cu, Pb and Zn. After Box-Cox transformation of the content values, TB was significantly different for As (4.82), Cd (3.84), Cu (2.95), Pb (4.38), and Zn (4.23). Multivariate factor analysis singled out four elemental associations: F1 (Al-Co-Cr-Fe-Li-Ni-V), F2 (Cd-Pb-Zn), F3 (Ca-Mg-Na-P) and F4 (Cu) with a total variance of 89%. Spatial distribution visualized the hazardously higher contents of "hot spots" of Cd > 1.30 mg/kg, Cu > 22 mg/kg, Pb > 130 mg/kg and Zn > 160 mg/kg. Therefore, main approach in moss biomonitoring should be based on data management of the element distribution by reducing the effect of extreme values (considering Box-Cox data transformation); the interspecies variation in sampling media does not deviate in relation to H. cupressiforme vs. C. lutescens.

Long-term Geochemical Evolution of Lithogenic Versus Anthropogenic Distribution of Macro and Trace Elements in Household Attic Dust.

Attic dusts were examined as historical archives of anthropogenic emissions, with the goal of elucidating the enrichment pathways associated with hydrothermal exploitation of Cu, Pb, and Zn minerals in the Bregalnica River basin in the eastern part of the Republic of Macedonia. Dust samples were collected from 84 settlements. Atomic emission spectrometry and mass spectrometry with inductively coupled plasma were applied as analytical techniques for the determination of 69 element contents. Multivariate analysis was applied for the extraction of dominant geochemical markers. The lithogenic distribution was simplified to six dominant geochemical markers: F1: Ga-Nb-Ta-Y-(La-Gd)-(Eu-Lu); F2: Be-Cr-Li-Mg-Ni; F3: Ag-Bi-Cd-Cu-In-Mn-Pb-Sb-Te-W-Zn; F4: Ba-Cs-Hf-Pd-Rb-Sr-Tl-Zr; F5: As-Co-Ge-V; and F6: К-Na-Sc-Ti. The anthropogenic effects on the air pollution were marked by a dominance of F3 and secondary dominance of F5. The fifth factor also was determined as a lithogenic marker for the occurrence of the very old Rifeous shales. The first factor also presents a very unique association that despite the heterogeneity relays on natural phenomena of tracking the deposition in areas of Proterosoic gneisses; related to the distribution of fine particles was associated with carbonate-silicate volcanic rocks. Intensive poly-metallic dust depositions were recorded only in the surroundings of localities where the hydrothermal extractions are implemented. Long-term deposition can be considered as pollution indexes for these hot spots. This mainly affects the Cd, Pb, and Zn deposition that is as high as 25, 3900, and 3200 mg/kg, respectively.