Abstract
In the framework of the International Cooperative Program on Effects of Air Pollution on Natural Vegetation and Crops (UNECE ICP Vegetation), in 2002, 2005, and 2010, a moss biomonitoring technique was applied to air pollution studies in the Republic of Macedonia. А fourth moss survey took place in August and September 2015, when 72 samples of the terrestrial moss samples were collected over the territory of the country. Using inductively coupled plasma-atomic emission spectrometry (ICP-AES) and atomic absorption spectrometry (AAS), a total of 22 elements (Al, As, Ba, Ca, Cd, Co, Cr, Cu, Fe, Hg, K, Li, Mg, Mn, Mo, Na, Ni, Pb, Rb, Sr, V, and Zn) were determined. By comparing the obtained values from all of the surveys, it can be concluded that almost all potentially toxic elements (As, Cd, Co, Cr, Cu, Ni, Pb, and Zn) increased in content in moss samples from 2002 to 2005 but decreased in the samples from 2010 to 2015. Increased values from 2005 to 2015 were observed for Cd and Pb, which is likely due to the reactivation of mining for lead and zinc in Eastern Macedonia, with large amounts of floatation tailings deposited in the landfills as well as due to the increased capacity of the ferronickel smelter near the city of Kavadarci. From data obtained in 2015, a factor analysis was performed to identify and characterize different pollution sources. Distributional maps for all elements were also prepared to point out the regions that were the most affected by anthropogenic activities. The survey conducted in 2015 showed that the situation with air pollution by potentially toxic metals in Macedonia is similar to that established in 2010. This is because all activities in the fields of mining and metallurgy were in continuous work with the same capacity during that five-year period. Still, the largest anthropogenic impact of air pollution with heavy metals established a smelter for ferronickel near Kavadarci (Ni and Cr) and lead and zinc mines in the vicinity of Probištip, Makedonska Kamenica, and Kriva Palanka (Cd, Pb, and Zn).
Similar content being viewed by others
References
Allajbeu S, Qarri F, Marku E, Bekteshi L, Ibro V, Frontasyeva M, Stafilov T, Lazo P (2017) Contamination scale on atmospheric deposition for assessing air quality in albania evaluated from most toxic heavy metal and moss biomonitoring. Air Qual Atmos Health 10:587–599
Angelovska S, Stafilov T, Šajn R, Bačeva K, Balabanova B (2014) Moss biomonitoring of air pollution with heavy metals in the vicinity of Pb-Zn mine “Toranica” near the town of Kriva Palanka. Modern Chem Appl 2(123):1–6
Angelovska S, Stafilov T, Šajn R, Balabanova B (2016) Geogenic and anthropogenic moss responsiveness on lithological elements distribution around Pb-Zn ore deposit. Arch Environ Contam Toxicol 70:487–505
Anttila P, Stefanovska A, Nestorovska-Krsteska A, Grozdanovski L, Atanasov I, Golubov N, Ristevski P, Toceva M, Lappi S, Walden J (2016) Characterisation of extreme air pollution episodes in an urban valley in the Balkan Peninsula. Air Qual Atmos Health 9:129–141
Arsovski M (1997) Tectonics of Macedonia. Faculty of Mining and Geology, Štip, pp 1–306
Bačeva K, Stafilov R, Šajn R (2009) Biomonitoring of nickel air pollution near the city of Kavadarci, Republic of Macedonia. Ecol Protect Environ 12:57–69
Bačeva K, Stafilov T, Šajn R, Tănăselia C (2012) Moss biomonitoring of air pollution with heavy metals in the vicinity of a ferronickel smelter plant. J Environ Sci Health A 47:645–656
Bačeva K, Stafilov T, Šajn R, Tănăselia C (2013) Air dispersion of heavy metals in vicinity of the As-Sb-Tl abounded mine and responsiveness of moss as a biomonitoring media in small scale investigations. Environ Sci Pollut Res 20:8763–8779
Balabanova B, Stafilov T, Bačeva K, Šajn T (2010) Bıomonıtorıng of atmospherıc pollutıon wıth heavy metals ın the copper mıne vıcınıty located near Radovıš. Republıc of Macedonıa J Environ Sci Health A 45:1504–1518
Balabanova B, Stafilov T, Šajn R (2014a) Variability assessment for multivariate analysis of elemental distributions due to anthropogenic and geogenic impact in lead-zinc mine and flotation environ (moss sampling media). Geol Maced 28:35–41
Balabanova B, Stafilov T, Šajn R, Bačeva Andonovska K (2017) Quantitative assessment of metal elements using moss species as biomonitors in downwind area of lead-zinc mine. J Environ Sci Health A 52:290–301
Balabanova B, Stafilov T, Šajn R, Bačeva K (2014b) Comparison of response of moss, lichens and attic dust to geology and atmospheric pollution from copper mine. Int J Environ Sci Technol 11:517–528
Balabanova B, Stafilov T, Šajn R, Tănăselia C (2016) Multivariate extraction of dominant geochemical markers for 69 elements deposition in Bregalnica River Basin, Republic of Macedonia (moss biomonitoring). Environ Sci Pollut Res 23:22852–22870
Barandovski L, Cekova M, Frontasyeva MV, Pavlov SS, Stafilov T, Steinnes E, Urumov V (2008) Atmospheric deposition of trace element pollutants in Macedonia studied by the moss biomonitoring technique. Environ Monit Assess 138:107–118
Barandovski L, Frontasyeva MV, Stafilov T, Šajn R, Pavlov S, Enimiteva V (2012) Trends of atmospheric deposition of trace elements in Macedonia studied by the moss biomonitoring technique. J Environ Sci Health A 47:2000–2015
Barandovski L, Stafilov T, Šajn R, Frontasyeva MV, Bačeva K (2013) Air pollution study in Macedonia by using moss biomonitoring technique, ICP-AES and AAS. Maced J Chem Chem Eng 32:89–107
Barandovski L, Frontasyeva MV, Stafilov T, Šajn R, Ostrovnaya T (2015) Atmospheric deposition of trace elements in Macedonia studied by the moss biomonitoring technique. Environ Sci Pollut Res 22(20):16077–16097 (2015)
Buse A, Norris D, Harmens H, Buker P, Ashenden T, Mills G (2003) Heavy metals in European mosses: 2000/2001 survey. UNECE ICP vegetation Programme coordination Centre. Centre for Ecology and Hydrology, Bangor, p 46
Čeburnis D, Šakalys J, Armolaitis K, Valiulis D, Kvietkus K (2002) In–stack emissions of heavy metals estimated by moss biomonitoring method and snow–pack analysis. Atmos Environ 36:1465–1474
Chakrabortty S, Paraktar GT (2006) Biomonitoring of trace element air pollution using mosses. Aerosol Air Qual Res 6:247–258
Cohen J (1988) Statistical power analysis for the behavioral sciences, Second edn. Lawrence Erlbaum Associates Publishers, New York
Davis JC (1986) Statistic and data analysis in geology. Willey & Sons, New York
Dimovska B, Šajn R, Stafilov T, Bačeva K, Tănăselia C (2014) Determination of atmospheric pollution around the thermoelectic power plant using a moss biomonitoring. Air Qual Atmos Health 7:541–557
Dimovska B, Stafilov T, Šajn R, Tănăselia C (2013) Moss biomonitoring of air pollution with arsenic in Bitola and its environs, republic of Macedonia. Geol Maced 27:5–11
Dmuchowski W, Bytnerowicz A (2009) Long-term (1992–2004) record of lead, cadmium, and zinc air contamination in Warsaw. Poland: determination by chemical analysis of moss bags and leaves of Crimean linden. Environ Poll 157:3413–3421
Dumurdžanov N, Serafimovski T, Burchfiel BC (2004) Evolution of the Neogene-Pleistocene Basins of Macedonia. Geological Society of America Digital Map and Chart Series 1 (accompanying notes), Boulder, Colorado, p 20
Dumurdžanov N, Serafimovski T, Burchfield BC (2005) Cenozoic tectonics of Macedonia and its relation to the South Balkan extensional regime. Geosphere 1:1–22
Dumurdžanov N, Serafimovski T, Burchfiel BC (2008) Genesis and lithostratigraphy of Neogene and Pleistocene basins in Macedonia. Proceedings on the First Congress of Geologists of the Republic of Macedonia, Ohrid, pp 21–52
Garson D (2000) Factor analysis. PA 765: quantitative research in public administration. North Carolina State University, Raleigh
Harmens H, Buse A, Büker P, Norris D, Mills G, Williams B (2004) Heavy metal concentrations in Europeanmosses: 2000/2001 survey. J Atmos Chem 49:425–436
Harmens H, Noris D, Aboal-Viñas J, Alber R, Aleksiayenak Y, Ashmore M, Barandovski L, Berg T, Bermejo R, Blum O, Carballeira Ocaña A, Çayir A, Cokun Ma, Cokun Mü, Dam M, Dieffenbach-Fries H, Elustondo D, Ermakova E, Fernández Escribano A, Florek M, Frolova M, Frontasyeva MV, Godzik B, González-Miqueo L, Grodziska K, Jarvis K, Jeran Z, Jordan C, Kapusta P, Karhu J, Krmar M, Kubin E, Kvietkus K, Lasheras E, Leblond S, Liiv S, Lloyd A, Makovská B, Marinova S, Magnússon SH, Meresova J, Nikodemus O, Olsson T, Oszlanyi J, Pankratova Y, Piipa-nen J, Poikolainen J, Traubenberg Rauschde C, Riss A, Rühling Å, Santamaría JJM, Schröder LW, Spiric Z, Stafilov T, Steinnes E, Strelkova Ly, Suchara I, Sucharová J, Szarek-Ukaszewska G, Szymon K, Thöni L, Temmerman D, Uggerud H, Urumov V, Yurukova L, Vergel K, Zechmeister H (2008) Spatial and temporal trends in heavy metal accumulation in mosses in Europe (1990–2005) Harmens H and Noris D, eds., Programme Coordination Centre for the ICP Vegetation, Centre for Ecology & Hydrology, Natural Environment Research Council: Bangor. International Cooperative Programme on Effects of Air Pollution on Natural Vegetation and Crops (2005) Heavy metals in European mosses: 2005/2006 survey. Monitoring manual. Centre for Ecology & Hydrology, Natural Environment Research Council, Bangor, UK, http://icpvegetation.ceh.ac.uk/publications.htm
Harmens H, Norris DA, Steinnes E, Kubin E, Piispanen J, Alber R, Aleksiayenak Y, Blum O, Coşkun M, Dam M, De Temmerman L, Fernández JA, Frolova M, Frontasyeva M, González-Miqueo L, Grodzińska K, Jeran Z, Korzekwa S, Krmar M, Kvietkus K, Leblond S, Liiv S, Magnússon SH, Maňkovská B, Pesch R, Rühling A, Santamaria JM, Schröder W, Spiric Z, Suchara I, Thöni L, Urumov V, Yurukova L, Zechmeister HG (2010) Mosses as biomonitors of atmospheric heavy metal deposition: spatial and temporal trends in Europe. Environ Pollut 158:3144–3156
Harmens H, Mills G, Hayes F, Norris D, Aboal JR, Ahmad SS, Alber R, Alonso R, Aleksiayenak Y, Amadou HI, Barandovski L et al (2013) Air pollution and vegetation. In: Harmens H, Mills G, Hayes F, Norris D (eds) ICP vegetation annual report 2012/2013, ICP vegetation Programme coordination Centre, Centre for Ecology and Hydrology. Environment Centre Wales, Deiniol road, Bangor
Harmens H, Mills G, Hayes F, Sharps K, Frontasyeva M (Eds.) (2014) Air pollution and vegetation ICP vegetation annual report 2013/2014. International Cooperative Programme on Effects of Air Pollution on Natural Vegetation and Crops, Centre for Ecology & Hydrology, Natural Environment Research Council, Bangor, UK
Harmens H, Norris DA, Sharps K, Mills G, Alber R, Aleksiayenak Y, Blum O, Cucu-Man SM, Dam M, De Temmerman L, Ene A, Fernández JA, Martinez-Abaigar J, Frontasyeva M, Godzik B, Jeran Z, Lazo P, Leblond S, Liiv S, Magnússon SH, Maňkovská B, Phil-Karlsson G, Piispanen J, Poikolainen J, Santamaria JM, Skudnik M, Spiric Z, Stafilov T, Steinnes E, Stihi C, Suchara I, Thöni L, Todoran R, Yurukova L, Zechmeister HG (2015) Heavy metal and nitrogenconcentrations in mosses are declining across Europe whilst some “hotspots” remain in2010. Environ Pollut 200:93–104
Hristozova G, Marinova S, Pavlovna Strelkova L, Goryainova Z, Frontasyeva MV, Stafilov T (2014) Atmospheric deposition study in the area of Kardzhali lead-zinc plant based on moss analysis. Am J Anal Chem 5:920–931
ICP Vegetation (2010) Heavy metals in European mosses: 2010 survey. Monitoring manual. International Cooperative Programme on Effects of Air Pollution on Natural Vegetation and Crops. Centre for Ecology & Hydrology, Natural Environment Research Council, Bangor, UK, http://icpvegetation.ceh.ac.uk/publications.htm
Karagjuleva J, Kostandinov V, Zogarcev I (1974) Tectonic characteristic of the Kraistides. In: Mahel M (ed) Tectonics of the Carphathian Balkan regions. Geological Institute of Dionyz Štur, Bratislava, pp 332–340
Kuang YW, Zhou GY, Wen DZ, Liu SZ (2007) Heavy metals in bark of Pinus Massoniana (lamb.) as an indicator of atmospheric deposition near a smeltery at Qujiang, China. Environ Sci Pollut Res 14:270–275
Lazarevski A (1993) Climate in Macedonia. Kultura, Skopje (In Macedonian)
Pendžerkovski Ј (1976) Interpreter of the geological map of 1:200,000 of SR Macedonia. Professional fund of the Geological Survey of Macedonia, Skopje
Pendžerkovski Ј, Hadži-Mitrova S (1977) Interpreter of the geological map of SR Macedonia 1:200,000. Professional fund of the Geological Survey of Macedonia, Skopje
Qarri F, Lazo P, Stafillov T, Frontasyeva M, Harmens H, Bekteshi L, Baceva K, Goryainova Z (2014a) Multi-elements atmospheric deposition study in Albania. Environ Sci Pollut Res 21:2506–2518
Qarri F, Lazo P, Stafilov T, Bekteshi L, Baceva K, Marka J (2014b) Survey of atmospheric deposition of Al, Cr, Fe, Ni, V and Zn in Albania by using moss biomonitoring and ICP-AES. Air Qual Atmos Health 7:297–307
Rühling Å, Steinnes E (eds.) (1998) Atmospheric heavy metal deposition in Europe 1995–1996, NORD environment 1998, Vol. 15, Nordic Council of MinistryCopenhagen
Šajn R (2005) Using attic dust and soil for the separation of anthropogenic and geogenic elemental distributions in an old metallurgic area (Celje, Slovenia). Geochem Explor Env A 5:59–67
Šajn R (2006) Factor analysis of soil and attic-dust to separate mining and metallurgy influence, Meža Valley, Slovenia. Math Geol 38:735–747
Shakya K, Chettri MK, Sawidis T (2008) Impact of heavy metals (copper, zinc, and lead) on the chlorophyll content of some mosses. Arch Environ Contam Toxicol 54:412–421
Špirić Z, Vučković I, Stafilov T, Kušan V, Frontasyeva V (2013) Air pollution study in Croatia using moss biomonitoring and ICP–AES and AAS analytical techniques. Arch Environ Contam Toxicol 65:33–46
Stafilov T, Šajn R, Pančevski Z, Boev B, Frontasyeva MV, Strelkova LP (2010a) Heavy metal contamination of surface soils around a lead and zinc smelter in the Republic of Macedonia, J. Hazard Mater 175:896–914
Stafilov T, Šajn R, Boev B, Cvetković J, Mukaetov D, Andreevski M, Lepitkova S (2010b) Distribution of some elements in surface soil over the Kavadarci region, Republic of Macedonia. Environ Earth Sci 61:1515–1530
Stafilov T (2014) Environmental pollution with heavy metals in the Republic of Macedonia. Contrib Sect Nat Math Biotech Sci MASA 35:81–119
Stafilov T, Šajn R (2016) Geochemical atlas of the Republic of Macedonia. Faculty of Natural Sciences and Mathematics, Skopje
Stafilov T, Šajn R, Ahmeti L (2017) Geochemical atlas of Skopje. Faculty of Natural Sciences and Mathematics, Skopje
Steinnes E, Rühling Å, Lippo H, Mäkinen A (1997) Reference materials for large-scale metal deposition surveys. Accred Qual Assur 2:243–249
Steinnes E, Uggerud HT, Pfaffhuber KA, Berg T (2016) Atmospheric deposition of heavy metals in Norway–national moss survey 2015. М–595. Norwegian Institute for Air Research, Trondheim
Zechmeister HG (1995) Correlation between altitude and heavy metal deposition in the Alps. Environ Pollut 89:73–80
Zhang C, Selinus O, Schedin J (1998) Statistical analyses for heavy metal contents in till and root samples in an area of southern Sweden. Sci Total Environ 212:217–232
Acknowledgements
The authors acknowledge the financial support from the Slovenian Research Agency (research core funding No. P1-0020 - Groundwaters and geochemistry.
Author information
Authors and Affiliations
Corresponding author
Rights and permissions
About this article
Cite this article
Stafilov, T., Šajn, R., Barandovski, L. et al. Moss biomonitoring of atmospheric deposition study of minor and trace elements in Macedonia. Air Qual Atmos Health 11, 137–152 (2018). https://doi.org/10.1007/s11869-017-0529-1
Received:
Accepted:
Published:
Issue Date:
DOI: https://doi.org/10.1007/s11869-017-0529-1