Journal of Hazardous Materials 175 (2010) 896–914 Contents lists available at ScienceDirect Journal of Hazardous Materials journal homepage: www.elsevier.com/locate/jhazmat Heavy metal contamination of topsoils around a lead and zinc smelter in the Republic of Macedonia Trajˇ ce Stafilov a,∗ , Robert ˇ Sajn b , Zlatko Panˇ cevski a , Blaˇ zo Boev c , Marina V. Frontasyeva d , Lyudmila P. Strelkova d a Institute of Chemistry, Faculty of Science, Sts. Cyril and Methodius University, P.O. Box 162, 1001 Skopje, Republic of Macedonia b Geological Survey of Slovenia, Dimiˇ ceva ul. 14, 1000 Ljubljana, Slovenia c Faculty of Natural and Technical Sciences, Goce Delˇ cev University, ˇ Stip, Republic of Macedonia d Frank Laboratory of Neutron Physics, Joint Institute for Nuclear Research, 141980 Dubna, Moscow Region, Russian Federation article info Article history: Received 27 March 2009 Received in revised form 21 October 2009 Accepted 22 October 2009 Available online 31 October 2009 Keywords: Soil Heavy metals Pollution Veles Republic of Macedonia abstract The results of a first systematic study of spatial distribution of different elements in surface soil over the Veles region (50 km 2 ) known for its lead and zinc industrial activity in the recent past are reported. A total of 201 soil samples were collected according to a dense net in urban area and less dense net in rural area. The total of 42 elements were analyzed by epithermal neutron activation analysis (ENAA) and by atomic absorption spectrometry (AAS). The content of elements such as As, Au, Cd, Cu, Hg, In, Pb, Sb, Se, Zn in soil samples around the lead and zinc smelter and in the adjacent part of the town of Veles has appeared to be much higher than in those collected in the surrounding areas due to the pollution from the plant. Thus, the content of Cd (three times); Pb and Zn (two times) is even higher than the corresponding intervention (critical) values according to the Dutch standards. The results obtained by two complementary analytical techniques, AAS and ENAA, are discussed in terms of multivariate statistics. GIS technology was applied to depict the areas most affected by contamination from the lead and zinc smelter. © 2009 Elsevier B.V. All rights reserved. 1. Introduction The human impact on the biosphere has been very broad and complex, and most often has led to irreversible changes. All human- made changes disturb the natural balance of each ecosystem that has been formed evolutionarily over a long period of time. Thus, these changes most often lead to a degradation of the natu- ral human environment. Urban pollution with heavy metals has recently become a subject of many studies [1–13]. The regional con- tamination of soil occurs mainly in industrial regions and within centres of large settlements, where factories, motor vehicles and municipal wastes are the most important sources of trace metals [1]. Because of the heterogeneity and ceaseless changing of urban areas, it is necessary first to understand the natural distribution and the methods for distinguishing human-made anomalies in nature. The natural background itself is variable, which means that higher concentrations of some elements can be considered normal for one region but abnormal for another. However, there are cases when the industrial enterprises, especially mining and metallurgical plants, situated near cities can increase the pollution. It is obvious from the ∗ Corresponding author. Tel.: +389 2 3249 906; fax: +389 2 3226 865. E-mail address: trajcest@pmf.ukim.mk (T. Stafilov). articles published recently that lead and zinc mines and smelter plants activities lead to enormous soil contamination [14–22]. The intent of this article is to present the results of a first sys- tematic study of spatial distribution of different chemical elements in surface soil in the Veles region in the Republic of Macedonia, known for its lead and zinc industrial activity in the nearest past. There were several investigations of soil, vegetables and fruits pro- duced in the region of Veles, but they were mainly concerned with contamination by lead, zinc and cadmium [23–27]. Other elements were not determined though it is known that the minerals of many other heavy metals (As, Sb, In, Cu, etc.) are present in lead and zinc ore and concentrates used for the production of Pb and Zn in the smelter plants [28,29]. For this reason the goal of this work was to determine as many elements as possible in the soil from the town of Veles and its surroundings, and to assess the size of the area affected by the lead and zinc smelter plant situated nearby. For this purpose, a total of 201 soil samples were collected from a dense grid (0.25 km and 0.5 km) in the urban area, and less dense grid (1 km) in the rural area. The most characteristic elements for the given industrial activity (Cu, Cd, Zn, Hg and Pb) were determined by atomic absorption spectrometry (AAS), and a set of other 39 ele- ments (Al, Ca, Fe, K, Mg, Na, Ti, As, Au, Ba, Br, Ce, Co, Cr, Cs, Cu, Dy, Hf, In, La, Mn, Mo, Nd, Ni, Rb, Sb, Sc, Se, Sm, Sr, Ta, Tb, Th, Tm, U, V, W, Yb and Zn) by epithermal neutron activation analysis (ENAA). 0304-3894/$ – see front matter © 2009 Elsevier B.V. All rights reserved. doi:10.1016/j.jhazmat.2009.10.094