1. Moss biomonitoring of the distribution of chemical elements in the air in the Prespa region, North MacedoniaBiljana Dimkova, Robert Šajn, Trajče Stafilov, 2024, original scientific article Abstract: A study was conducted to investigate atmospheric deposition and to explore the natural distribution and possible contamination with potentially toxic elements (PTEs) in the Prespa region, North Macedonia, using moss samples as biomonitors for air pollution. The distribution of 19 chemical elements (Ag, Al, Ba, Ca, Cr, Cu, Fe, K, Li, Mg, Mn, Mo, Na, Ni, P, Pb, Sr, V, and Zn) was detected in 11 moss samples from this area. The moss samples were analysed after microwave digestion using inductively coupled plasma – atomic emission spectrometry (ICP-AES). R-mode factor analysis was used to identify and characterise the elemental associations, and four associations of elements were identified. Four factors were separated from the group of elements: Factor 1 (Fe-Al-Cr-V-Ni), Factor 2 (Sr-Ba-Mg), Factor 3 (K-P-Zn) and Factor 4 (Pb-Cu). All element factors were found to be typical geochemical associations, with the exception of the distribution of K and P in the agricultural areas of the study area where fertilisers are used over a long period of time. Keywords: moss biomonitoring, air pollution, potentially toxic elements, Prespa region, North Macedonia Published in DiRROS: 25.07.2024; Views: 118; Downloads: 119
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2. Investigations of chemical element distributions in soil, North Macedonia—a reviewTrajče 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: 451; Downloads: 225
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3. Moss as a biomonitor to identify atmospheric deposition of minor and trace elements in MacedoniaRobert Šajn, Katerina Bačeva Andronovska, Trajče Stafilov, Lambe Barandovski, 2024, original scientific article Abstract: 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). Keywords: moss, atmospheric deposition, trace elements, air quality, Macedonia Published in DiRROS: 20.03.2024; Views: 573; Downloads: 391
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4. Assessment of atmospheric deposition of potentially toxic elements in Macedonia using a moss biomonitoring techniqueLambe Barandovski, Trajče Stafilov, Robert Šajn, Katerina Bačeva Andronovska, Marina V. Frontasyeva, Inga Zinicovscaia, 2024, original scientific article Abstract: 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. Keywords: moss, biomonitoring, air pollution, potentially toxic elements, Macedonia Published in DiRROS: 06.02.2024; Views: 361; Downloads: 127
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5. Multivariate statistical methods in determining the spatial distribution of chemical elements in soil from the Mavrovo-Rostuše region, North MacedoniaTrajče 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: 451; Downloads: 115
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6. Distribution of chemical elements in surface waters from the Strumica River Basin, North MacedoniaKaterina Trajanova, Robert Šajn, Trajče Stafilov, 2023, original scientific article Abstract: In this work, the distribution of chemical elements in samples of surface water from the Strumica River Basin, North Macedonia, was studied. The water samples were collected from a total of twelve sites. In addition to the Strumica River, samples were collected from its tributaries: Bansko, Dabile, Turija, Vodoča, Radoviška, and Injevska. The determination of the concentration of 21 elements (Ag, Al, Ba, Ca, Cd, Co, Cr, Cu, Fe, K, Li, Mg, Mn, Mo, Na, Ni, P, Pb, Sr, V, and Zn) was performed by inductively coupled plasma - atomic emission spectrometry (ICP-AES). All detailed information on the studied items was statistically processed using Stat Soft, 11.0 software. Using the obtained data on the concentration of the studied elements, descriptive statistical analysis of the values for the concentration of the elements was performed. A map of spatial distribution was obtained for each element. The obtained results show that the concentrations of the studied elements in the surface water samples are relatively low and the distribution of most of the elements follows the lithology of the study area. Keywords: rivers, surface water, heavy metals, Strumica River Basin, North Macedonia Published in DiRROS: 20.07.2023; Views: 539; Downloads: 169
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7. Next-generation sequencing to characterize pyrazinamide resistance in Mycobacterium tuberculosis isolates from two Balkan countriesEva Sodja, Simon Koren, Nataša Toplak, Sara Truden, Marija Žolnir-Dovč, 2021, original scientific article Abstract: Objectives. Next-generation sequencing (NGS) provide a comprehensive analysis of the genetic alterations that are most commonly linked with pyrazinamide (PZA) resistance. There are no studies reporting molecular background of PZA resistance in TB isolates from Balkan Peninsula. We aimed to examine the feasibility of full-length analysis of a gene linked with PZA resistance, pncA, using Ion Torrent technology in comparison to phenotypic BACTEC MGIT 960 DST in clinical TB isolates from two countries of the Balkan Peninsula. Methods. Between 1996 and 2017, we retrospectively selected 61 TB isolates. To identify gene variants related to drug resistance in genomic DNA extracted from TB isolates, AmpliSeq libraries were generated automatically using the AmpliSeq™ Kit for Chef DL8 and the Ion AmpliSeq TB Research Panel. Result.s Of all 61 TB isolates included, 56 TB were phenotypically resistant to any antibiotic. Among them, 38/56 (67.9%) TB isolates were phenotypically resistant to pyrazinamide and pncA mutations were detected in 33/38 cases (86.8%). A mutation in the pncA promoter region was the most prevalent genetic alteration, detected in eight TB isolates. Comparison of NGS to conventional BACTEC MGIT 960 DST revealed very strong agreement (90.2%) between the two methods in identifying PZA resistance, with high sensitivity (89.5%) and specificity (95.7%) for NGS. Conclusions. Detection of PZA resistance using NGS seems to be a valuable tool for surveillance of TB drug resistance also in the Balkan Peninsula, with great potential to provide useful information at least one weak earlier than is possible with phenotypic DST. Keywords: tuberculosis, Mycobacterium tuberculosis, high-throughput nucleotide sequencing, pyrazinamide, microbial sensitivity tests, next-generation sequencing, drug susceptibility testing, Slovenia, Republic of North Macedonia Published in DiRROS: 10.01.2022; Views: 1180; Downloads: 701
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8. Hereditary angioedema due to C1-inhibitor deficiency in Macedonia : clinical characteristics, novel SERPING1 mutations, and genetic factors modifying the clinical phenotypeVesna Grivčeva-Panovska, Mitja Košnik, Peter Korošec, Slađana Andrejević, Ljerka Karadža-Lapić, Matija Rijavec, 2018, original scientific article Abstract: Objective: Hereditary angioedema due to C1 inhibitor deficiency (C1-INH-HAE) is a rare disease, characterized by swellings. We aimed to characterize on a clinical and molecular basis C1-INH-HAE patients in the Republic of Macedonia. Results: All 15 patients from six unrelated families were diagnosed with C1-INHHAE type I, with a mean age of symptom onset of 11 years and an average delay of diagnosis of 7 years. Patients reported on average 31 angioedema attacks/year, with a median clinical severity score (CSS) of 7. We identified three known mutations, and two mutations (c.813_818delCAACAA and c.1488T>G) were reported for the first time. To address the genotype-phenotype association, a pooled analysis including 78 C1-INH-HAE south-eastern European patients was performed, with additional analysis of F12-46C/T and KLKB1- 428G/A polymorphisms. We demonstrated that patients with nonsense and frameshift mutations, large deletions/insertions, splicing defects, and mutations at Arg444 exhibited an increased CSS compared with missense mutations, excluding mutations at Arg444. In addition, the CC F12-46C/T polymorphism was suggestive of earlier disease onset. Discussion: Genetic analysis helped identify the molecular basis of C1-INH-HAE given that causative mutations in SERPING1 were detected in all patients, including an infant before the appearance of clinical symptoms. We identified two novel mutations and further corroborated the genotype-phenotype relationship, wherein mutations with a clear effect on C1-INH function predispose patients to a more severe disease phenotype and CC F12-46C/T predisposes patients to earlier disease onset. Keywords: hereditary angioedemas -- genetics -- Macedonia, C1 inhibitor, SERPING1 gene, C1 inhibitor, SERPING1 gene Published in DiRROS: 30.11.2020; Views: 1445; Downloads: 339
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