GEOLOGIJA 49/1, 123–132, Ljubljana 2006 Influence of ironworks on distribution of chemical elements in Bosnia and Herzegovina and Slovenia Vpliv ‘elezarn na porazdelitev kemi~nih prvin v Bosni in Hercegovini ter Sloveniji Jasminka ALIJAGI]1 & Robert [AJN2 1Masaryk University of Brno, Faculty of Science, Kotlarska 2, 61137, Brno, Czech Republic e-mail: j.alijagic@yahoo.co.uk 2Geological survey of Slovenia, Dimi~eva 14, 1000 Ljubljana, Slovenia e-mail: robert.sajn@geo-zs.si Key words: ironworks, pollution, attic dust, soil, Bosnia and Herzegovina, Slovenia Klju~ne besede: ‘elezarne, onesna‘enje, podstre{ni prah, tla, Bosna in Hercegovina, Slovenija Abstract The objective of this work is the study of the distribution of chemical elements in attic dust and topsoil for the identification of anthropogenic and geogenic element sources in an old metallurgic area in Bosnia and Herzegovina and Slovenia (Slo – BiH bilateral project “Heavy metals in environment as consequences of mining and smelting in the past”). Samples of attic dust and topsoil were collected in localities in BiH (Zenica, Vare{ and Ilija{) and Slovenia (Jesenice, [tore and Ravne). Analysis for 42 chemical elements was performed. Based on a comparison of statistical parameters, spatial distribution of particular elements and results of cluster analysis one natural and two anthropogenic geochemical associations were identified. The natural geochemical association (Al-K-La-Sc-Th-Ti) is influenced mainly by lithology. The anthropogenic association (Co-Cr-Mo-Ni-V-W) is the result of iron metallurgy in the past. The second anthropogenic association (Ag-As-Cd-Fe-Hg-Mn-Pb-Sb-Sn-Zn) is the result of high level of sulphide phase in iron ore (Vare{) and zinc and sulphuric acid production in the Celje area. Povzetek Namen pri~ujo~ih raziskav je {tudij porazdelitve kemi~nih prvin v podstre{nem prahu in tleh za ugotavljanje in lo~evanje naravnih in antropogeno povzro~enih porazdelitev kemi~nih prvin na obmo~jih intenzivnega ‘elezarstva v Bosni in Hercegovini ter v Sloveniji (Slo-BiH bilateralni projekt “Te‘ke kovine v okolju kot posledica rudarjenja in topilni{tva v preteklosti”). V ta namen smo zbrali vzorce podstre{nega prahu in tal na petnajstih lokacijah v Bosni in Hercegovni (Zenica, Vare{ in Ilija{) ter v Sloveniji (Jesenice, [tore in Ravne). Vzor~ni material je bil analiziran na 42 kemi~ne prvine. Na osnovi primerjave stati-sti~nih parametrov, porazdelitve posameznih prvin in rezultatov clusterske analize smo izlo~ili eno naravno ter dve anropogeno povzro~eni geokemi~ni asociaciji. Porazdelitev Al-K-La-Sc-Th-Ti je predvsem posledica vpliva litolo{ke podlage. Antropogeno povzro~ena asociacija (Co-Cr-Mo-Ni-V-W) je nastala zaradi delovanja ‘elezarstva v preteklosti. Naslednja antropogeno povzro~ena asociacija (Ag-As-Cd-Fe-Hg-Mn-Pb-Sb-Sn-Zn) je rezultat visokega dele‘a sulfidne faze v ‘elezovi rudi (Vare{) ali pa pridelave cinka in ‘veplove kisline na obmo~ju Celja. 124 Introduction The objective of this work is the study of the distribution of chemical elements in attic dust and topsoil for the identification of anthropogenic (man-made) and geogenic (natural) element sources in an old metal-lurgic area in Bosnia and Herzegovina and Slovenia (Slo – BiH bilateral project “Heavy metals in environment as consequences of mining and smelting in the past”). Samples of attic dust and topsoil were collected in localities in BiH (Zenica, Vare{ and Ilija{) and Slovenia (Jesenice, [tore and Ravne). In previous geochemical studies ([ajn, 1999; 2003) the properties of attic dust as a sampling medium for the territory of Slovenia (regional-scale) were established. The applicability of attic dust and topsoil for tracing the mercury halo in the Idrija area (Gosar & [ajn, 2001; Gosar & [ajn, 2003) and pollution of heavy metals in Celje ([ajn , 2005), Me‘ica ([ajn et al., 2000; [ a j n , 2002) and Jesenice area ([ a j n et al., 1998) was successfully proven. The basic idea of the project is the hypothesis that relations between geogenic and anthropogenic chemical elements in sampling media, especially in attic dust, are preserved in wider regional scale regardless of architectonic particularity of attics in the region and lithology. We believe that this research has proven it. Geographical and geological description of study areas Localities in Slovenia (Fig. 1) Celje ([tore) The town of Celje is situated in the central part of Slovenia. In the area of the Celje - [tore urban zone live about 55,000 inhabitants (Anton~i~ , 2001). The industry is concentrated in the eastern part of the Celje town. The Zinc smelter Celje, started its operation in 1873 and is still in operation today. It has been estimated 580,000 tons of zinc were produced between the years 1875 and 1970 (@ibret, 2002). The construction of the ironworks [tore started in 1856. The [tore ironworks was a relatively large operation from the beginning. Production and processing were in ex- Jasminka Alijagi} & Robert [ajn pansion until 1991, after that the production dropped radically. In the geological sense, the studied area represents a young tectonic basin. It is filled with Quaternary deposits of the Savinja, Vo-glajna and Hudinja rivers. In the northern part are Pleistocene clays, quartz gravel and sand. Tuff and marine clay of the Oligocene age underlie these deposits. In the southeast part also Miocene sand, sandstone, marly limestone and lithothamnian limestone are exposed, as a part of the Celje syncline. The oldest rocks (shale, limestone, keratophyre and keratophyre tuff of the Ladinian age, and Upper Triassic massive limestone) crop out in the southern part (Buser, 1977). Jesenice The Jesenice area is situated in the northwest part of Slovenia (Fig. 1). The administrative, political and economic centre is the town of Jesenice, a typical industrial town with iron making tradition, inhabited by a population of about 20,000. Iron making in the Jesenice area is traditional. The deve- Figure 1. Locations of observed ironworks in Bosnia and Herzegovina and Slovenia Slika 1. Lokacije ‘elezarn v Bosni in Hercegovini ter Sloveniji Influence of ironworks on distribution of chemical elements in Bosnia and Herzegovina and... 125 lopment of mines and furnaces started end of 14th century as testified by the Ortenburg mining regulations (http://www.jesenice.si/ jeobc.html). After WWII Jesenice became the center of black metallurgy in Slovenia. Introduction of electrical steel processing marked the era of manufacturing steel of higher quality and in greater quantities. At its peak in 1970s, the ironworks employed more than 8,000 people (http://psychcentral.com/psypsych/je-senice). The territory is situated at the contact of three geotectonic units: the south Karavanke, the Ljubljana basin and the Julian Alps. The central ridge of Karavanke is built by the Ko{uta nappe that consists predominantly of carbonate rocks of Lower to Upper Triassic age. The southern Karavanke nappe, in the area between the Ko{uta nappe and the Sava fault, consists mostly of Paleozoic clastic and carbonate rocks. The Ra-dovljica-Bled subsided basin in the southeast is filled by Quaternary deposits in the extreme part of the Ljubljana basin. In the southeast, the Me‘akla plateau consists of Lower to Upper Triassic carbonate rocks (Buser & Cajhen , 1980; Jurkov{ek , 1986). Ravne The research area lies in the northern part of Slovenia, close to the Austrian border (Fig. 1). The Meza river valley cuts in its upper part through the Eastern Karavanke Mts., and in its lower parts, the settlements Pre-valje and Ravne are placed. After the year 1835, ironworking had developed at Prevalje and later at Ravne (M o-hori~, 1954). The Me‘a valley is strongly polluted with heavy metals due to mining and smelting. The major pollutants are lead and zinc, which were being extracted in the upper part of the Me‘a valley for more than 300 years ([ajn et al., 2000; Vre~a et al., 2001). Ironwork located in the lower part of the valley also contributed to the pollution of the area during a 150-year operating period (Souvent, 1994). The upper part of the valley cuts mostly through Triassic limestone and dolomite. The lower part of the valley cuts through metamorphic rocks (Mio~ et al., 1983). Localities in Bosnia and Herzegovina (Fig 1.) Zenica Zenica is an industrial city of 130,000, distanced 70 kilometers north from the capital Sarajevo, by the valley of the river Bosna (http://bs.wikipedia.org/wiki/zenica). Construction of the iron and steelworks in Zenica started in 1892, but already in 1899, the iron and steel works produced about 3700 tons of rolled products. In 1940, the iron and steel works produced 1/3 of the total production of steel and rolled production of Yugoslavia. By putting a new facilities into operation and expansion of production continued in 1986 and reached record of 1,720,000 tons of pig iron and 1,906,000 tons of crude steel. In April 1992, production was stopped but in 1998 emerged a new company called “BH STEEL Company” (http://www.bhsteel.com.ba/istorija.htm). The city of Zenica is situated in valley that is covered by alluvium of the Bosna River, partly on alluvial terrace sediments. On the West side of the Bosna River, Miocene and Oligocene rocks outcrop and comprise clays, sandstones, conglomerates and marls thought to represent post-orogenic shelf sediments of Pannonian Sea. On the East side of the Bosna River are Upper Cretaceous massive limestones and limestone breccias and on top is flysch (@ivanovi} et al., 1975). Vare{ This small city is situated in a valley of the river Stavnja with 20,000 inhabitants. In region of Vare{, iron ore mined and smelted from Antique period. With arrival Austrians to Bosnia, Vare{ admire revival in economy aspect. Iron work of Vare{ is established in 1891, and operated until 1991. Before last war, Vare{ had been forcefully industrial centre, but from that time, mining and metallic activities are stopped (http://bs.wiki-pedia.org/wiki/vares; http://zeljezara-va-res.com/onama.html). The oldest rocks are Triassic age sandstone and sandy shale and massive, thick-bedded limestone. There is a part with Anisian limestones and dolomites, bearing hematite 126 and siderite. The abandoned mine in Vare{ was the biggest Fe mine in Bosnia and Herzegovina. The mine zone is represented by carbonates and iron oxide minerals. Moreover, Pb and Zn deposits are reported within the same sequence. In the Vare{ area, Pb-Zn mineralization is connected with the Fe deposit. (O l u j i } et al., 1978). Ilija{ Ilija{ is a municipality located about 20 km north east of the city of Sarajevo. As per dates in 2002, in a district of Ilija{ have lived 15,000 inhabitants. Ironwork of Ilija{ begun with production in 1954, and in time developed in giant who spread around 60 ha. Now, production stagnates. Pre war number of employed decreased from 3,500 on approximately 200 (http://bs.wikipedia.org/wiki/ ilijas; http://www.geocities.com/suceska 2003/aktilijas.htm). The ironwork Ilija{ is situated on Quaternary sediments. Rocks in the Ilija{ basin are Miocene and Oligocene ages, same as in the town Zenica (Jovanovi} et al., 1978). Materials and methods Sampling design and materials Samples were collected from three localities in Bosnia and Herzegovina (Zenica, Va-re{ and Ilija{) and in Slovenia (Jesenice, Ravne and [tore) (Fig. 1). In each Slovenian locality we collected three samples and from each Bosnian locality, two samples. In total we sampled fifteen localities, and at each we collected topsoil (0-5 cm) and attic dust. Close to each sample site location an old house was chosen with intact attic carpentry. Most of the selected houses were at least 100 years old. To avoid collecting particles of tiles, wood and other construction materials, the attic dust samples were brushed from parts of wooden constructions that were not in immediate contact with roof tiles or floors. Soil was sampled from the surface to the depth of 5 cm close to the house in which attic dust was collected. Within the town, urban soil, such as soil in the gardens and on grass verges was sampled ([ajn, 2003; 2005). Jasminka Alijagi} & Robert [ajn Preparation of samples and analysis All samples were air-dried. The size fraction of attic dust smaller than 0.125 mm was prepared for chemical analyses by sieving. Soil samples were gently crushed then the fraction smaller than 2 mm was pulverized (Darnley et al., 1995; Salminen et al., 2005). Analysis for 41 chemical elements (Al, Ca, Fe, K, Mg, Na, P, S, Ti, Ag, As, Au, Ba, Be, Bi, Cd, Ce Co, Cr, Cu, Hf, La, Li, Mn, Mo, Nb, Ni, Pb, Rb, Sb, Sc, Sn, Sr, Ta, Th, U, V, W, Y, Zn and Zr) was performed by inductively coupled plasma mass spectrometry (ICP-MS) after (total) four-acid digestion (mixture of HClO4, HNO3, HCl and HF at 200oC). Hg was determined with cold vapor atomic absorption spectrometry CV-AAS after aqua region digestion (mixture HCl, HNO3 and water at 95oC). All samples, replicates and geologic standards were submitted to the laboratory in a random order. This procedure assured unbiased treatment of samples and random distribution of possible drift of analytical conditions across all samples. Sensitivity, accuracy and precision of analysis The sensitivity in the sense of the lower limit of detection was adequate for 36 out of 42 determined chemical elements. The elements Au, Be, Bi, Hf, Ta and W, however, were removed from further statistical analysis, (Miesch, 1976) since their contents in the majority of analyzed samples were below the lower detection limit of the analytical method. Accuracy of the analytical method for the remaining 36 elements was estimated by calculation of the relative systematic error between the determined and recommended values of geological standards. Most elements show, in the range of the actual samples, very low deviations. The means of elements in the standards generally differ by less than 15% of the recommended values. Results and discussion In these analyses we excluded some elements because some of them have concen- Influence of ironworks on distribution of chemical elements in Bosnia and Herzegovina and... 127 trations below detection limits, but some of them did not show any connection to other elements in multivariate statistical analyses. Consequently 22 elements (Tab. 1) used in the final statistical treatment. Number of samples for making a cluster analysis is small, but significant enough. Principally, no geochemical variations compare to other previous similar analysis. Based on a comparison of statistical parameters (Tab. 1), results of cluster analysis (Fig. 2) and calculated enrichment ratios (Tab. 2), one natural and two anthropogenic geoche-mical associations were identified. The natural geochemical association (Al-K-La-Sc-Th-Ti) is influenced mainly by lithology. The first anthropogenic association (Co-Cr-Mo-Ni-V-W) is the result of iron metallurgy in the past. The second anthropogenic association (Ag-As-Cd-Fe-Hg-Mn-Pb-Sb-Sn-Zn) is the result of high level of sulphide phase in iron ore (Vare{) and zinc and sulphuric acid production in the Celje area. First group: naturally distributed elements The first group links Al, K, La, Th, Ti and Sc. Characteristics for this geochemical group are high values of correlation coefficients (Tab. 3a) and results of Cluster analyses (Fig. 2) between analyzed chemical elements. For these elements it is important to note that their average concentrations in topsoil are around 80% concentration in Slovenian soil. Concentration ratios vary between 0.5 and 1.2 (Tab. 2, Fig. 3). Highest concentrations were found in two areas, Ravne and [tore, and are a consequence of weathering of igneous rocks in their environment. The average of these elements in attic dust is 50% (varying between 0.3 and 0.7) concentration in Slovenian soil (Tab. 2, Fig.4). The highest ratio between attic dust and topsoil was found in the Ilija{ area (0.9) and the lowest in the Ravne area (0.4) (Tab. 2, Fig.5). Table 1. Slovenian averages in topsoil ([ a j n , 2003) and average values of 22 selected chemical elements for considered ironworks (Concentrations of Al, Fe, K and Ti are expressed in %, remaining elements in mg/kg) Tabela 1. Slovenska povpre~ja v tleh ([ a j n , 2003) ter povpre~ne vrednosti 22 izbranih kemi~nih prvin glede na obravnavano ‘elezarno (Vsebnosti Al, Fe, K in Ti so izra‘ene %, vsebnosti ostalih prvin v mg/kg) Topsoil (0-5 cm) Attic dust Element Slo Jesenice [tore Ravne Zenica Vare{ Ilija{ Jesenice [tore Ravne Zenica Vare{ Ilija{ First group of elements Al 6.9 5.1 6.0 7.1 4.2 4.0 4.2 2.4 3.0 2.6 3.0 2.3 4.1 K 1.6 1.2 1.8 1.9 1.0 1.0 1.1 0.66 1.0 0.76 0.59 0.79 1.2 La 32 23 35 34 24 22 39 9.0 15 15 12 16 22 Sc 12 10 10 15 9.0 10 6.7 5.3 7.0 5.0 7.0 Th 11 8.3 10 11 7.3 5.6 7.4 4.7 4.3 3.7 4.7 3.3 7.5 Ti 0.33 0.22 0.30 0.25 0.24 0.27 0.23 0.10 0.29 0.12 0.16 0.12 0.23 Second group of elements Co 16 9.0 12 22 16 25 34 14 16 42 19 32 17 Cr 91 242 99 574 161 271 166 445 354 3327 156 194 218 Mo 0.80 7.0 2.5 33 1.8 5.2 5.5 22 26 214 5.4 16 7.6 Ni 50 83 53 130 133 187 114 211 144 604 181 144 92 V 102 79 98 124 80 91 89 76 107 162 89 82 74 W 1.4 2.0 2.3 26 1.5 6.5 4.7 2.7 6.7 186 2.8 24 5.6 Third group of elements Ag 0.090 0.58 0.20 0.30 1.0 2.6 0.45 2.1 1.7 8.5 4.0 6.1 0.35 As 14 19 28 20 57 31 91 44 116 28 121 83 44 Cd 0.45 1.9 4.9 2.1 1.5 3.5 1.8 5.8 37 6.2 4.3 9.0 1.6 Fe 3.5 5.3 4.7 5.7 4.5 7.6 11 13 14 13 8.6 19 6.8 Hg 0.070 0.59 0.63 0.22 0.51 1.1 5.4 2.6 1.8 0.29 1.8 3.6 0.99 Mn 1054 2320 976 1292 1284 3704 2674 6089 2418 2792 2598 5173 1310 Pb 42 430 175 500 267 918 166 1651 1368 1223 982 2412 199 Sb 1.1 2.5 2.0 5.7 11 29 8.3 12 15 17 52 85 7.7 Sn 3.1 8.3 5.7 12 6.5 20 12 17 27 39 14 58 14 Zn 124 828 706 1431 441 2434 361 2200 6835 1911 1204 5830 453 128 Jasminka Alijagi} & Robert [ajn Table 2: Average enrichment ratios of group of elements according considered ironworks Tabela 2: Povpre~na obogatitvena razmerja skupin kemi~nih prvin glede na obravnavano ‘elezarno Group 1 Group 2 Group 3 Location X, Xg Min - Max X, – Xg Min - Max X – Xg Min - Max Enrichment ratio (M topsoil/M s lovenian average ) Jesenice 0.75 (0.67 - 0.81) 1.7 (0.56 - 8.7) 3.6 (1.3 - 10) [tore 0.97 (0.86 - 1.1) 1.3 (0.77 - 3.2) 3.5 (0.93 - 21) Ravne 1.1 (0.78 - 1.3) 5.3 (1.2 - 42) 3.7 (1.2 - 12) Zenica 0.70 (0.61 - 0.75) 1.4 (0.78 - 2.7) 3.8 (1.2 - 12) Vare{ 0.67 (0.53 - 0.83) 2.8 (0.89 - 6.5) 9.0 (2.2 - 31) Ilija{ 0.79 (0.62 - 1.2) 2.4 (0.67 - 6.8) 5.6 (2.5 - 82) Average 0.82 (0.53 - 1.2) 2.2 (0.56 - 42) 4.6 (0.93 - 82) Enrichment ratio (M attic dust/M slovenian average ) Jesenice 0.37 (0.28 - 0.44) 3.0 (0.74 - 28) 11 (3.2 - 41) [tore 0.56 (0.41 - 0.88) 3.5 (1.0 - 32) 15 (2.3 - 82) Ravne 0.42 (0.35 - 0.48) 20 (1.6 - 267) 10 (2.0 - 100) Zenica 0.45 (0.37 - 0.58) 2.1 (0.87 - 6.7) 11 (2.5 - 47) Vare{ 0.40 (0.31 - 0.51) 3.9 (0.80 - 20) 22 (4.9 - 77) Ilija{ 0.67 (0.58 - 0.73) 2.2 (0.72 - 9.4) 4.1 (1.2 - 15) Average 0.48 (0.28 - 0.73) 4.0 (0.72 - 267) 11 (1.2 - 100) Enrichment ratio (M attic dust/M topsoil ) Jesenice 0.49 (0.40 - 0.56) 1.8 (0.95 - 3.1) 3.0 (2.0 - 4.9) [tore 0.58 (0.43 - 0.95) 2.7 (1.1 - 10) 4.3 (0.67 - 9.7) Ravne 0.40 (0.34 - 0.47) 3.8 (1.3 - 7.2) 2.7 (1.3 - 28) Zenica 0.65 (0.51 - 0.78) 1.5 (0.97 - 3.1) 2.8 (1.9 - 4.9) Vare{ 0.61 (0.44 - 0.78) 1.4 (0.72 - 3.7) 2.5 (1.4 - 3.2) Ilija{ 0.88 (0.57 - 1.0) 0.95 (0.49 - 1.4) 0.74 (0.18 - 1.3) Average 0.60 (0.34 - 1.0) 1.8 (0.49 - 10) 2.7 (0.18 - 28) X - mean (srednja vrednost); Xg - geometric mean (geometri~na srednja vrednost) Min – minimum (minimum); Max – maximum (maksimum) Whereas these elements are not included in technological processes of ironworks, we presume that the source of the above elements in topsoil and attic dust is natural, i.e. they originate from soil dust and represent the natural state. Based on these ratios, we can roughly evaluate that the lowest polluti- on is in the Ilija{ area and the highest in the Ravne area. Similar relationships have been determined during previous research of soil and attic dust in Celje ([ajn, 2005), Jesenice ([ajn, 1998) and Ravne ([ajn , 2002) areas. It is proposed that the distribution of most elements is related to bedrock. Figure 2. Dendrogram of cluster analysis (15 samples of each attic dust and topsoil; 22 selected elements) Slika 2. Dendrogram clusterske analize (po 15 vzorcev podstre{nega prahu in tal; 22 izbranih kemi~nih prvin) Influence of ironworks on distribution of chemical elements in Bosnia and Herzegovina and... 129 Figure 3. Concentration ratios of groups of elements in topsoil with regard to location of sampling Slika 3. Koncentracijska razmerja skupin kemi~nih prvin v tleh v odvisnosti od lokacije vzor~enja Fig. 5. Concentration ratios (attic dust/topsoil) of groups of elements with regard location of sampling Slika 5.Koncentracijska razmerja (podstre{ni prah/tla) skupin kemi~nih prvin v odvisnosti od lokacije vzor~enja Figure 4. Concentration ratios of groups of elements in attic dust with regard to location of sampling Slika 4. Koncentracijska razmerja skupin kemi~nih prvin v podstre{nem prahu v odvisnosti od lokacije vzor~enja Second group: anthropogenically introduced siderophile elements The second group links mainly siderophi-le elements: Mo, Ni, Co, W, V, and Cr. As with the previous group, high values are observed for correlation coefficients (Tab. 3b), reinforced by results of Cluster analyses (Fig. 2) between analyzed chemical elements. For these elements it is significant that their average concentration ratio in topsoil exceeds the average for Slovenian soil by a factor of around 2.2. Concentration ratios vary between 0.6 and 42 (Tab. 2, Fig. 3). The highest concentration is again in the Ravne area. The average of these elements in attic dust exceeds by a factor of 4 average for Slovenian soil (variation is between 0.7 and 267). Again, the highest concentration is in the Ravne area (Tab. 2, Fig. 4). As in first group, the highest ratio between attic dust and topsoil is found in the Ravne area (3.8) and lowest in the Ilija{ area (0.95) (Tab. 2, Fig. 5). From this, it is possible to conclude that the consequences of mining are most pronounced in Ravne and least pronounced in Ili-ja{. However, ironwork in Ilija{ has a shorter history than in the other five localities. Similar relationships have been determined during previous research of soil and attic dust in the areas Celje ([ajn , 2005), Jesenice ([ajn et al., 1998) and Ravne ([ajn, 2002). Table 3a. Correlation coefficients (r) between geogenic elements (n=30; P0.05, 28=0.361) Tabela 3a. Korelacijski koeficienti (r) med geogenimi kemi~nimi prvinami (n=30; P =0.361) 8 Al K Ti La Sc Th Al 1.00 K 0.90 1.00 Ti 0.75 0.68 1.00 La 0.78 0.79 0.61 1.00 Sc 0.96 0.86 0.74 0.76 1.00 Th 0.95 0.85 0.66 0.77 0.89 1.00 130 Jasminka Alijagi} & Robert [ajn Third group: anthropogenically introduced chalcophile elements This group links Ag, As, Cd, Pb, Zn, Sb, Sn, Hg, and two siderophile elements Fe and Mn. In this group, as with the two previous groups, we observe a strong relationship between correlation coefficients (Tab. 3c) and results of Cluster analyses (Fig. 2) between analyzed chemical elements. The highest enrichments are in topsoil, in attic dust and in ratios attic dust/topsoil. In topsoil, the average concentration is 4.6 times higher than in average Slovenian soil (highest concentration is in Vare{ and lowest in [tore) (Tab. 2, Fig.3). The average of these elements in attic dust exceeds by a factor of 11 the average for Slovenian soil (varying from 1.2 to 100). The highest concentration of these elements (22) is found in the Vare{ area, and basically represents the maximum for this group (Tab. 2, Fig.4). The highest ratio between attic dust and topsoil Table 3b. Correlation coefficients (r) between anthropogenically introduced siderophile elements (n=30; P0.05, 28=0.361) Tabela 3c. Korelacijski koeficienti (r) med antropogeno vnesenimi siderofilnimi kemi~nimi prvinami (n=30; P0.05, 28=0.361) Co Cr Mo Ni V W Co 1.00 Cr 0.56 1.00 Mo 0.48 0.84 1.00 Ni 0.70 0.86 0.68 1.00 V 0.53 0.68 0.46 0.58 1.00 W 0.68 0.74 0.85 0.61 0.49 1.00 is found in the [tore area and, as with the two previous groups, the lowest in the Ilija{ area (Tab. 2, Fig.5). The high content of the aforesaid group of elements in the Vare{ area is consequence of the appearance of Pb-Zn. Metallurgical processes considerably increased the content of sulphide elements in all sampled materials and caused serious environmental pollution. A few kilometers west of the [tore is the town of Celje ([ajn, 2005), where there was an old Zn smelter (over 100 years old), that contributed to a high concentration of chalcophile elements. Conclusion Based on these analyses, we can compare pollution levels in each of these six ironworks. We have found that in the cities Zenica and Vare{ there exist high concentrations of chalcophile and siderophile elements. Because of this it is very important to continue with further research on these two localities. In the Ilija{ area, by contrast, the pollution level is very low and, for now, further research will be discontinued. In the Vare{ area there is a very high concentration of chalcophile elements, which originate from ore deposits. This ironwork had a major influence on soil, stream sediments and stream terraces of the River Stavnja. My future work will focus more on this area. It is also very important to continue with research in the city of Zenica, because this Table 3c. Correlation coefficients (r) between anthropogenically introduced chalcophile elements (n=30; P0.05, 28=0.361) Tabela 3c. Korelacijski koeficienti (r) med antropogeno vnesenimi halkofilnimi kemi~nimi prvinami (n=30; P0.05, 28=0.361) Fe Ag As Cd Mn Pb Sb Sn Zn Hg Fe 1.00 Ag 0.67 1.00 As 0.62 0.53 1.00 Cd 0.65 0.47 0.46 1.00 Mn 0.77 0.72 0.41 0.42 1.00 Pb 0.75 0.80 0.39 0.71 0.75 1.00 Sb 0.67 0.82 0.62 0.43 0.58 0.74 1.00 Sn 0.73 0.69 0.39 0.61 0.56 0.78 0.78 1.00 Zn 0.68 0.62 0.35 0.86 0.60 0.88 0.62 0.77 1.00 Hg 0.66 0.45 0.75 0.34 0.64 0.40 0.48 0.31 0.34 1.00 Influence of ironworks on distribution of chemical elements in Bosnia and Herzegovina and... 131 ironwork is the largest in the Balkans, and there is a prominent metallurgical tradition. Based on the results, we can expect high pollution both siderophile and chalcophile elements. This two, in Zenica and Vare{ and several other industrial giants are situated in the valley of the River Bosna. It would be very important to check the content of these elements in its stream sediments, as well as alluvial plains where there are intensive agricultural activities. This may have a huge influence on human health and groundwa-ter. Acknowledgements The governments of the Slovenia and Bosnia and Herzegovina financed the project. We would like to thank to Geological Survey of Slovenia that help with data processing. But the authors would like to express our gratitude to all of them who participated in the project, especially to all kind people who allowed us out of their good will to take samples in their attics and gardens. References A n t o n ~ i ~ , A. 2001: Statistical yearbook -Statistical office of the Republic of Slovenia, Ljubljana. B u s e r , S. & C a j h e n , J. 1980: Basic geological map of SFRJ, sheet Celovec 1:100.000. - Federal Geological Survey, Beograd. D a r n l e y , A. G., B j ö r k l u n d , A., B o l v i -k e n , B., Gustavsson, N., Koval , P. V., Plant , J. 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