Distribution of Chemical Elements in an Old Metallurgic Area, Zenica (Central Bosnia)

MASARYK UNIVERSITY OF BRNO Faculty of Science

Jasminka Alijagić

Distribution of chemical elements in an old Metallurgic area, Zenica (Central Bosnia)

Master dissertation

Supervisor: Doc. RNDr. Josef Zeman, CSc. Consultant: Dr. Robert Šajn

Brno, 2007

DECLARATION

With this declaration, I would like to say that I was working myself on this Master dissertation, and I was using the literature, which is listed in the references of this work.

Brno, 15. 05. 2007 ......

3 Name and surname: Jasminka Alijagić Title of the Master thesis: Distribution of chemical elements in an old Metallurgic area, Zenica (Central Bosnia) Study program: Geology Field of study: Geology Supervisor: Doc. RNDr. Josef Zeman, CSc. Year of defence: 2008

Annotation: The Master thesis is made within researches, which are achieved in territory of Bosnia and Herzegovina under bilateral project between Geological survey of Slovenia and Faculty of Natural Sciences, at University of Sarajevo (BI-BA/04-05-009) in period 2004 - 06.

The objective of this work is the study of the distribution of chemical elements in topsoil and bottom soil for the identification of anthropogenic (man-made) and geogenic (natural) element sources in an old metallurgic area on a local scale. At 62 different sites, samples of attic dust, topsoil (0-5 cm depth) and bottom soil (20-30 cm depth) have collected in 52 km2 of the Zenica area. Analysis for 42 chemical elements has performed. Based on a comparison of statistical parameters, spatial distribution of particular elements and results of cluster and factor analysis, two natural and one anthropogenic geochemical associations were identified.

Two natural geochemical associations (Al, Ca, Ce, K, La, Li, Nb, Rb, Sc, Ta, Ti Th, V and Y) and (Co, Cr, Na, Ni and Mg) are influenced mainly by lithology. The third anthropogenic associations (Ag, Bi, Cd, Cu, Hg, Mo, Pb, Sb and Zn) are the result of iron metallurgy in the past. Based on chemical analyzes, pollution of Zenica municipality with heavy metals such as As, Cd, Co, Cr, Cu, Hg, Ni, Pb and Zn, have been performed regard to the world and Slovenian law regulations. Natural processes influence high concentrations, priory of Ni and Cr but also Co. Pollution with As, Cd, Cu, Hg, Pb and Zn are consequences of anthropogenic activities.

KEYWORDS: pollution; topsoil; bottom soil; heavy metals; Zenica; Bosnia and Herzegovina

ACKNOWLEDGEMENTS

I would like to express my gratitude to all those who gave me the possibility to complete this dissertation.

I want to thank the Faculty of Science, the Department of Geological Sciences, the governments of the Slovenia and Bosnia and Herzegovina who financed the project. I have furthermore to thank the Geological survey of Slovenia that provided me improvement in area of geochemistry and help with data processing.

I am deeply indebted to my supervisor doc. RNDr. Josef Zeman, CSc. Whose helped and supported me in my study and research work.

Especially, I would like to give my special thanks to Dr. Robert Šajn from the Geological Survey of Slovenia whose help, stimulating suggestions and encouragement helped me in all the time of research for and writing of this thesis.

The author would like to express her gratitude to all of them who participated in the project, especially to all the people who allowed us out of their good will to take samples in their attics and gardens.

5 CONTENTS

1. INTRODUCTION ...... 13 1.1. THE GOALS OF THE MASTER THESIS ...... 14

2. GENERAL PART ...... 15 2.1. POLLUTION ...... 15 2.1.1. Definition ...... 15 2.1.2. Spot pollution ...... 15 2.1.3. Linear pollution ...... 15 2.1.4. Diffuse pollution ...... 15 2.2. HEAVY METALS IN SOIL ...... 16 2.2.1. Definition of soil and soil formation ...... 16 2.2.2. Heavy metals and soil ...... 17 2.2.3. Soil contamination ...... 18 2.2.4. Sources of heavy metals in soil ...... 18 2.2.5. Determining of critical value of heavy metals in soil sediment ...... 19 2.3. HEAVY METALS IN ATTIC DUST ...... 20 2.3.1. Definition of dust ...... 20 2.3.2. Definition of attic dust ...... 22

3. DESCRIPTION OF STUDY AREA ...... 24 3.1. GEOGRAPHICAL DESCRIPTION ...... 24 3.2. GEOLOGICAL DESCRIPTION ...... 28 3.2.1. Mesozoic ...... 28 3.2.2. Cenozoic ...... 28 3.2.2.1. Oligo - Miocene complex (Ol,M) ...... 28 3.2.2.2. Older Miocene complex (M2,3) ...... 30 3.2.2.3. Quaternary (Q) ...... 30 3.2.3. Tectonic...... 31 3.3. PEDOLOGICAL DESCRIPTION ...... 31 3.3.1. Automorphic soils ...... 31 3.3.2. Hydromorphic soils ...... 32 3.3.3. Anthropogenic soils ...... 32 3.4. HISTORY OF IRONWORKING IN ZENICA AREA ...... 32 3.5. REWIEV OF PREVIOUS RESEARCH IN ZENICA AREA ...... 34

4. MATERIAL AND METHODS ...... 36 4.1. SAMPLING DESIGN ...... 36 4.2. SAMPLING MATERIAL ...... 38 4.2.1. Soil sampling ...... 38 4.2.2. Attic dust sampling ...... 40 4.3. PREPARATION OF SAMPLES ...... 40 4.4. ANALYTICAL METHODS ...... 41 4.4.1. Analysing of chemical elements (ICP-MS) ...... 41 4.4.2. Analysing of Mercury (ASS-CV) ...... 42

5. RESULTS ...... 43 5.1 DATA MATRIX ...... 43 5.2. RELIABILITY OF ANALYSES ...... 43 5.2.1. Detection limit ...... 43 5.2.2. Accuracy ...... 44 5.2.3. Precision ...... 45 5.3. DATA PROCESSING ...... 46 5.3.1. Statistical methods ...... 46 5.3.1.1. Basic multivariate statistics and normality of distribution ...... 46 5.3.1.2. Bivariate statistics (correlations) ...... 49 5.3.1.3. The multivariate statistical method ...... 50 5.3.1.4. Enrichment ratio ...... 53 5.3.1.5. Map of elements areal distribution ...... 55

6. DISCUSSION ...... 56 6.1. NATURAL DISTRIBUTION OF CHEMICAL ELEMENTS ...... 56 6.2. ANTHROPOGENIC DISTRIBUTION OF CHEMICAL ELEMENTS ...... 61 6.3. DISTRIBUTION OF PARTICULAR HEAVY METALS IN SOIL ...... 64 6.3.1. Arsenic (As) ...... 64 6.3.2. Cadmium (Cd) ...... 67 6.3.3. Cobalt (Co) ...... 70 6.3.4. Chromium (Cr) ...... 73 6.3.5. Cooper (Cu) ...... 76 6.3.6. Mercury (Hg) ...... 79 6.3.7. Nickel (Ni) ...... 82 6.3.8. Lead (Pb) ...... 85 6.3.9. Zinc (Zn) ...... 88 6.4. SOIL POLLUTION OF ZENICA AREA ...... 91

7. CONCLUSION ...... 96 8. REFERENCES ...... 98 8.1. HTTP SOURCES ...... 101

7 CONTENT OF TABLES

Table 1: The New Dutchlist ...... 19 Table 2: Critical, warning and limit values of heavy metals in Slovenia...... 20 Table 3: Concentrations of heavy metals in soil (Ivetić, 1991; Goletić, 2001)...... 35 Table 4: Detection limits of analysed elements (ACME, 2005-2006) ...... 44 Table 5: Basic statistics of the chemical elements in topsoil (0-5 cm); n =60...... 47 Table 6: Basic statistics of the chemical elements in bottom soil (20-30 cm); n=60...... 48 Table 7a: Matrix of correlation coefficients (r) of selected 14 chemical elements - First group (n=120)...... 49 Table 7b: Matrix of correlation coefficients (r) of selected 5 chemical elements - Second group (n=120) ...... 50 Table 7c: Matrix of correlation coefficients (r) of selected 9 chemical elements - Third group (n=120) ...... 50 Table 8: Matrix of dominant rotated factor loadings (n=120, 28 selected elements)...... 52 Table 9: Slovenian averages in topsoil (Šajn, 2003) and average values of seven selected chemical elements (Alijagić & Šajn, 2006) for considered ironworks in Slovenia and B&H...... 94

8 CONTENT OF FIGURES

Figure 1: Sources of atmospheric dust (Fergusson, 1992)...... 21 Figure 2: Sources of surface dust (Fergusson, 1992)...... 22 Figure 3: Location of study area in Bosnia and Herzegovina...... 24 Figure 4: The town Zenica in Austro-Hungarian period ...... 26 Figure 5: The town Zenica today...... 26 Figure 6: Generalized land use map of study area...... 27 Figure 7: Generalized geological map of study area ...... 29 Figure 8: The ironworks in Austro-Hungarian period...... 33 Figure 9: The ironworks today...... 34 Figure 10: Map of sampling locations with interpolated area ...... 37 Figure 11: An example of soil profile...... 38 Figure 12: Soil sampling...... 39 Figure 13: Attic dust sampling ...... 39 Figure 14: Preparation of samples (I) ...... 40 Figure 15: Preparation of samples (II)...... 41 Figure 16: Accuracy of analysed chemical elements...... 45 Figure 17: Precision of analysed chemical elements...... 46 Figure 18: Tree diagram of cluster analysis (n=120, 28 selected elements)...... 51 Figure 19: Enrichment ratios: attic dust versus topsoil (0-5 cm) – 28 selected elements...... 54 Figure 20: Enrichment ratios: topsoil (0-5 cm) versus bottom soil (20-30 cm) – 28 selected elements...... 55 Figure 21: Enrichment ratios of the first group of chemical elements according to lithology...... 57 Figure 22: Enrichment ratios of the second group of chemical elements according to lithology...... 58 Figure 23: Spatial Factor 1 scores (Al, Ce, K, La, Li, Nb, Rb, Sc, Ta, Ti, Th, V, Y and -Ca) distribution in the topsoil (above) and the bottom soil (below) ..... 59 Figure 24: Spatial Factor 3 scores (Co, Cr, Na, Ni and Mg) distribution in the topsoil (above) and the bottom soil (below)...... 60 Figure 25: Enrichment ratios of the second group of chemical elements according to land use...... 61 Figure 26: Spatial Factor 2 scores (Ag, Ba, Bi, Cd, Cu, Hg, Mo, Pb, Sb and Zn) distribution in the topsoil (above) and the bottom soil (below) ...... 62 Figure 27: Spatial arsenic distribution in topsoil (above) and bottom soil (below) ...... 65 Figure 28: Spatial arsenic pollution in topsoil (above) and bottom soil (below) according to the Slovenian legislation (Ur. List RS 68/96) ...... 66 Figure 29: Spatial cadmium distribution in topsoil (above) and bottom soil (below)...... 68 Figure 30: Spatial cadmium pollution in topsoil (above) and bottom soil (below) according to the Slovenian legislation (Ur. List RS 68/96) ...... 69 Figure 31: Spatial cobalt distribution in topsoil (above) and bottom soil (below)...... 71 Figure 32: Spatial cobalt pollution in topsoil (above) and bottom soil (below) according to the Slovenian legislation (Ur. List RS 68/96) ...... 72 Figure 33: Spatial chromium distribution in topsoil (above) and bottom soil (below) ...... 74 Figure 34: Spatial chromium pollution in topsoil (above) and bottom soil (below) according to the Slovenian legislation (Ur. List RS 68/96) ...... 75 Figure 35: Spatial copper distribution in topsoil (above) and bottom soil (below)...... 77 Figure 36: Spatial copper pollution in topsoil (above) and bottom soil (below) according to the Slovenian legislation (Ur. List RS 68/96) ...... 78

9 Figure 37: Spatial mercury distribution in topsoil (above) and bottom soil (below) ...... 80 Figure 38: Spatial mercury pollution in topsoil (above) and bottom soil (below) according to the Slovenian legislation (Ur. List RS 68/96) ...... 81 Figure 39: Spatial nickel distribution in topsoil (above) and bottom soil (below)...... 83 Figure 40: Spatial nickel pollution in topsoil (above) and bottom soil (below) according to the Slovenian legislation (Ur. List RS 68/96) ...... 84 Figure 41: Spatial lead distribution in topsoil (above) and bottom soil (below) ...... 86 Figure 42: Spatial lead pollution in topsoil (above) and bottom soil (below) according to the Slovenian legislation (Ur. List RS 68/96) ...... 87 Figure 43: Spatial zinc distribution in topsoil (above) and bottom soil (below) ...... 89 Figure 44: Spatial zinc pollution in topsoil (above) and bottom soil (below) according to the Slovenian legislation (Ur. List RS 68/96) ...... 90 Figure 45: Spatial natural origin pollution in topsoil (above) and bottom soil (below) according to the Slovenian legislation (Ur. List RS 68/96) ...... 92 Figure 46: Spatial anthropogenical pollution in topsoil (above) and bottom soil (below) according to the Slovenian legislation (Ur. List RS 68/96) ...... 93 Figure 47: Average enrichment ratios (group of samples/Slovenian topsoil) of As, Cd, Cu, Hg, Mo, Pb and Zn with regard sampling location...... 94

10 1. INTRODUCTION

Mining and metallurgic activities on territory of Bosnia and Herzegovina are among the oldest actions. The earliest recorded evidence dates back to the Neolithic age. Mineral exploration and mine development are noticed in Medieval Bosnia (14th and 15th centuries). Throughout Bosnia lead, copper, and silver mines have opened. The most important mines were situated in middle Bosnia basin (Kamenica, Olovo, Dusina and Deževica) and in eastern Bosnia basin (Srebrenica and their surrounding). Silver mines attracted a significant number of foreigner entrepreneurs who established settlements, colonies, and caravan parks. Large natural resources – especially coalmines (Tuzla, Doboj, Banovići, Ugljevik, Gacko, Breza, Kakanj, Zenica etc.), Fe mines (the Majdan Mountain, Vareš, Ljubija) Pb and Zn mines (Olovo, Vareš and Srebrenica) bauxite mines (Bužim, Jajce, Mostar and Vlasenica) – led Bosnia to total prosperity. First ironworks, steelworks, and smelters were built during the Austro-Hungarian period. Between the two world wars, the stagnation of industrial production is noticed; anyway, during the Communism, industrialization of Bosnia and Herzegovina increased, and so did the city of Zenica as well. The long activity period of mines, ironworks and smelters caused significant environmental pollution with heavy metals.

Heavy metals such as As, Cd, Hg, Pb and Zn, that accumulates in soil or binds to dust particles which are important holder of heavy metals, are in top priority. Most metals in the soil upper layers appear in adsorbed form. Free ions go over to solution, become mobile and accessible to plants. They can go over to surface and groundwater. Pollution of soil is strongly endangering vegetation. High share of toxic substances can appear in plants, and through nutritive cycle reach human being. Particles of household dust that do not fall down on soil can accumulate directly in human organism through inhaling or ingestion and cause poisoning (Fergusson, 1992).

Present research is restricted to the region of Zenica, where metallurgic activities have had a long tradition. In the Bilateral project between Bosnia and Herzegovina and Slovenia, we want to show a content of the heavy metals in soil. Some increased content of chemical elements in soil is the consequence of natural background. Sources of heavy metals that influence environmental pollution are consequences of metallurgic and industrial activities, burning of fossil fuel and household.

11 1.1. THE GOALS OF THE MASTER DISSETRATION

• Distribution of chemical elements in attic dust, topsoil and bottom soil; • Determination of main geochemical groups and their spatial distribution in soil; • Identification, of geogenic (natural) geochemical background and anthropogenic (man-made) element sources; • Determination of the spatial pollution with heavy metals in topsoil and bottom soil.

12 2. GENERAL PART

2.1. POLLUTION

2.1.1. Definition

Pollution is an undesirable change of physical, chemical, or biological feature of natural environment, which is caused by human activities and which is harmful for human beings. Pollution particles infiltrate very easily in soil, water, and atmosphere. There are two types of pollutants: biodegradable pollutants (e.g. organic sewage) and non-biodegradable pollutants (e.g. heavy metals, pesticides, thermic pollution, photochemical smog, disposal of nuclear waste, etc).

2.1.2. Spot pollution

An area of spot pollution is much more contaminated than areas met with diffuse pollution; anyway, consequences of this kind pollution are only local. Examples of spot pollution are traffic, industrial and energy activity, various dumps and dumps waste materials (Yaron et al., 1996). Contents of heavy metals are very high and they decrease with distance (Mattigod & Page, 1983).

2.1.3. Linear pollution

Example of linear soil pollution is pollution alongside roads and railways. Intensity of pollution depends upon type and density of traffic, while meteorological factors influence scope of pollution in extant (dominant permanent winds) and relief.

2.1.4. Diffuse pollution

The most frequent cause for soil pollution with heavy metals is diffuse pollution, where soil is polluted over air, not only locally, but also in larger distance from source of pollution in the surroundings of industrial and urban centres (Yaron et al., 1996). Heavy metals are usually present in the air at low concentration, and they are less dangerous (Yaron et al., 1996).

13 Different emissions of substances to the air in gaseous, liquid, or solid state are transported by the air and fall on the soil surface according to time circumstances, there because of constant pollution accumulate in soil.

2.2. HEAVY METALS IN SOIL

2.2.1. Definitions of soil and soil formation

There are two definitions of soil (Gerrard, 2000):

• Soil is product of weathering and may or may not contain organic matter but quite often contain air and water. • Soil is natural body that contain mineral particles, organic matter, living organisms, water and air, and include physical, chemical, and biological processes.

Rocks and minerals change because of the processes of weathering, which typically cause mineral materials to disintegrate into smaller parts. The elements released as products of weathering may form new secondary minerals. Weathering products that are loose or not consolidated are called “soil.” Weathering can be accomplished by one or a combination of physical and chemical processes.

Physical weathering is the most pronounced in cold and dry climates. Physical processes include effects of temperature. Most notable is the force exerted by the expansion of water as it freezes. Another physical process is abrasion caused by bombardment of minerals by materials suspended in wind and flowing water. Finally, plant roots established in the crack of rocks often exert a force strong enough to cleave the rock.

Chemical weathering dominates in warm or moist climates. Worldwide, chemical weathering processes tend to be more important in soil formation than physical forces do. The processes include: oxidation and reduction (of great importance for iron-containing minerals), carbonation (dissolution of minerals in water that has been made acidic by carbon dioxide), hydrolysis (when water splits into hydrogen and hydroxide, and one or both components participate directly in the chemical process), and hydration (when water is incorporated into

14 the crystal structure of a mineral, changing mineral properties). Minerals differ greatly in their resistance to weathering.

Soil formation means the development of a particular soil in a particular place. Weathering produces unconsolidated mineral material that one would call “soil.” However, the formation of any given unique soil includes processes that continue to operate long after this unconsolidated material is formed. The products of weathering are the materials in which soils form. Soil materials are often transported vertically within the soil profile. Materials can be added (such as humus from plants or sediments added by wind or water) or can be lost (such as by erosion or by leaching through the soil profile). The unconsolidated material in which soils form is called “parent material”. The term “soil formation” implies the formation of soil horizons and other features in the parent material (http://jan.ucc.nau.edu/ doetqp/courses/ env320/lec3/ Lec3.html).

2.2.2. Heavy metals and soil

The heavy metals are group of elements having specific gravities greater than 5 g/cm3. To this group belong very toxic such as Pb, Cd, Hg, As and U which have negative influence on living organisms. Among them, exist also elements that are essential for the organisms such as Cu, Mn, Fe, Zn, Co, Cr, Se, B and Mo (Baudo, 1987).

Stumm & Morgan (1996) distinguish atmophile and lithophile heavy metals. As, Pb and Cd, which are easier transported by air than by water, belong to the first group. Because of that, the main source of environmental pollution with these elements is air transportation. The main representatives of lithophile heavy metals are Co, Cr and Mg, which are more likely transported by water than by air. For this reason, the main source of pollution with these elements is water transportation.

From a geochemical point of view, elements in the soil are present in form of organic and inorganic matter, adsorbed on minerals in soil or included in the structure of living organism (Adriano, 1986). Many properties such as pH, Eh, organic matter in soil, cation exchange processes, and part of clay minerals and oxides of Fe, Mn ad Al, affect on the mobility of heavy metals (Kebata-Pendias & Pendias, 1986).

15 Most of the metals in upper layer of soil are present in adsorbed form. Simple ions are changed into solution, become mobile and accessible to the plants. Some of the heavy metals are easily transported from surface to ground water (Kebata-Pendias & Pendias, 1986).

2.2.3. Soil contamination

Natural source of heavy metals is weathering of primary minerals, in which are present in minute amounts. High content of heavy metals are contained in slightly weathered sulphides. Their quick weathering is slowed by absence of oxygen that comes in rocks in very small concentrations (Alloway & Ayres, 1993).

Soil contamination is either solid or liquid hazardous substances mixed with the naturally occurring soil. Usually, contaminants in the soil are physically or chemically attached to soil particles or, if they are not attached, are trapped in the small spaces between soil particles. Soil contamination results when hazardous substances are either spilled or buried directly in the soil or migrate to the soil from a spill that has occurred elsewhere. For example, soil can become contaminated when small particles containing hazardous substances are released from a smokestack and are deposited on the surrounding soil as they fall out of the air. Another source of soil contamination could be water that washes contamination away from an area containing hazardous substances and deposits the contamination in the soil as it flows over or through it (http://www.epa.gov/superfund/students/wastsite/soilspil.htm).

2.2.4. Sources of heavy metals in soil

Sources of heavy metals in soil are divided into two groups (Yaron et al., 1996).

Natural sources: Heavy metals are natural part of minerals and rocks. During physical, chemical and biological weathering processes, heavy metals are extracted, but have not harm consequences on the environment. They enrich the soil by way of air transportation, volcano eruptions and other natural disasters, especially with fires.

Anthropogenic sources: Examples of anthropogenic pollution with heavy metals are represented by industrial emissions, gaseous and dust material from thermal power plants, fumes from houses and transport emission.

16 2.2.5. Determining of critical values of heavy metals in soil

European countries are using different methods for the determining of critical values and harmfulness of heavy metals on living organisms. Referent points are commonly used for the determination of soil contamination. Those points represent possible unpolluted soil areas, which have similar physical, chemical, and biological properties and are situated on the same bedrocks as the area that is being studied. Soil pollution is easily and properly defined with examples of referent and polluted locations.

In The New Dutchlist (Tab. 1) optimum and action values are given for sediments (http://www.contaminatedland.co.uk/std-guid/dutch-l.htm). In 1996, in Slovenia worth regulation of critical, warning and limit emission values of hazardous substances in soil were given (Tab. 2). “Limit values” represent density of individual dangerous substances in soil that cause such pollution where soil quality and soil fertility are not changed. Within a value both affect and influence on human health and environment are variable. “Warning values” represent density of individual dangerous substances in soil that probably cause harmful effects or influence on human health and environment. “Critical values” represent density of individual dangerous substances in soil that have harmful effects and influences on human health and environment. Polluted soils are not good for rising of plants and animals and water retention and filtration (Uradni list RS, 68/96).

Table 1: The New Dutch list

Metals Optimum value Action value (mg/kg) (mg/kg)

As 29 55 Ba 200 625 Cd 0.8 12 Cr 100 380 Co 20 240 Cu 36 190 Hg 0.3 10 Mo 10 200 Ni 35 210 Pb 85 530 Zn 140 720

17 Table 2: Critical, warning and limit values of heavy metals in Slovenia (Uradni list RS, 68/96)

Metals Limit value Warning value Critical value (mg/kg) (mg/kg) (mg/kg)

As 20 30 55 Cd 1 2 12 Co 20 50 240 Cr 100 150 380 Cu 60 100 300 Hg 0.8 2 10 Mo 10 40 200 Ni 50 70 210 Pb 85 100 530 Zn 200 300 720

2.3. HEAVY METALS IN ATTIC DUST

2.3.1. Definition of dust

The name “dust” is used in a variety of ways, and with different meanings. These range from the material that accumulates on the earth’s surface, such as on streets and in living and working environments, to the particulate material suspended in the atmosphere. The names used for the two materials will be “surface dust” and “atmospheric dust.” Both surface and atmospheric dusts are increasingly seen to be a hazard to human beings as they are a source of intake of toxic materials such as heavy metals (Fergusson, 1992).

Particles 0.005–0.1 µm in diameter are primary particles produced from high temperature combustion processes and gas condensation. The particles within the size range 0.1-1.0 µm are called fine and are the result of the accumulation of smaller particles. Finally particles with diameters >1 µm are called coarse and are the result of mechanical production (from soil, plants, sea salt, volcanoes, wind blown material, abrasion). About 40-50% comes from the crust and soil, 10% marine (dependent on the proximity to the ocean), 3-5% fossil fuel, 10- 15% transport emission, and the rest from other sources (Fergusson, 1992).

18 ATMOSPHERIC DUST

NATURAL ANTHROPOGENIC

→ Forest fire → Industrial emission → Crustal material → Domestic⁄ commercial → Vegetation emission emission → Rock⁄ crust → Combustion coal & oil degassing → Transport emission → Volcanic emission → Weathered material (concrete, paint)

Figure 1: Sources of atmospheric dust (Fergusson, 1992)

Eventually much of the atmospheric dust (Fig. 1) becomes surface dust either through dry deposit or washed out by precipitation. The rate at which this happens depends on a number of factors including density of the particles, meteorological factors, coagulation and condensation processes for atmospheric particles. These surface dusts will in most cases, contain contributions from material that had not been airborne, or at least that has been only for a short time, such as weathered buildings materials, soil, deposited litter, and large particles from traffic emissions (Fergusson, 1992). The two surface dusts most studied are street and household dust (Fig. 2).

Atmospheric particles are divided into different groups according to their size, shape, composition, colour, and equilibrium between gaseous and solid phase.

19 SURFACE DUST

STREET DUST HOUSEHOLD DUST

→ Transport → Industrial dust carried → Rubbish (litter) home → Industrial deposits wastes → Internal dust (litter, wear, → Decaying vegetation combustion, carpet) → Soil → Soil → Paint → Paint → Weathered building → Weathered building materials materials

Figure 2: Sources of surface dust (Fergusson, 1992)

According to their size, atmospheric particles are divided into three groups: • Nuclide particles - In this group we find particles with diameters <0.08 µm. there are formed during combustion or condensation gases after emission. Electrically charged particles have a large mobility and tend to merge into bigger particles. • Accumulation particles - Into this group we have particles with diameter between 0.08 and 2 µm. They are formed through coagulation processes, during changes from gaseous to solid state, during condensation volatile substances and soil weathering. • Coarse particles - Particles with diameter >2 µm belong to coarse fraction. Mostly they are formed during soil weathering and in this group spores and flower powder are included (http://www.epa.gov).

2.3.2. Definition of attic dust

The term “dust” usually refers to street dust and household dust (Culbard et al., 1988; Fergusson & Kim, 1991; Fergusson, 1992). However, other types have also been studied in the past. A particular type of household dust – the attic dust – is studied in this work. It

20 represents dust deposited in the attics abandoned by inhabitants, so that tenant influence is minimized. The attic dust is derived predominantly from external sources as aerosols deposit and as a result of soil dusting, and less from household activities (Šajn, 1999; Šajn, 2000). The attic dust as sampling material has the advantage that its composition remains constant, i.e. chemically unchanged, with time. Investigations of attic dust chemistry therefore reveal the average historical state of the atmosphere.

In previous geochemical studies (Šajn, 1999; Šajn, 2000; Šajn, 2003) the use of attic dust as a sampling medium for the territory of Slovenia (on a regional scale) was established. The applicability of attic dust and topsoil for tracing the mercury halo in the Idrija area (Gosar & Šajn, 2003; Gosar et al., 2006) and pollution of heavy metals in Celje area (Šajn, 2005), Mezica area (Šajn, 2006) and around Bosnia and Herzegovina ironworks (Alijagić & Šajn, 2006) was successfully proven.

The use of attic dust was successful also in tracing plutonium aureole in Nevada (Cizdziel, 1998; Cizdziel et al., 1999), which was a result of atomic bomb experiments.

21 3. DESCRIPTION OF STUDY AREA

3.1. GEOGRAPHICAL DESCRIPTION

Zenica is town located in the valley of the river Bosna, about 70 km north from the capital Sarajevo. Zenica, for many of its characteristics and features, is a specific urban and economic area. Its peculiarities originate from both its geographic location, since it is situated in the very centre (Fig. 3) of Bosnia and Herzegovina and the economic and social character of its development. The main rail and road communications pass through the river Bosna valley.

Figure 3: Location of study area in Bosnia and Herzegovina

22 Town is situated in one of the largest and most beautiful valleys in the middle part of the River Bosna and surrounded by mountains and hills. The Zenica valley itself is stretching from Lašva canyon in the south, to Vranduk canyon to the north. Municipality of Zenica bordering with municipalities of Travnik, Vitez and Busovača on the West, Kakanj on the South, the mountains Ravan and Zvijezda on the East and on the North with municipality of Žepče. The urban area is located on alluvial terraces, on 316 m of altitude, surrounded with high hills from both sides of the valley with, height difference approximately between 300 and 1000 m. Left side of the valley is surrounded by hills Gaj, Okrumak, Brdo, Kozarci, Grm, Jezero, with villages Pridražići, Jakovići, Podbrežje, Raspotočje, Gnusi, and Drivuša. Right side of the valley is surrounded by hills Gaje, Strmica, Klopče brdo, Klopačke stijene and villages D.Vraca, D. Gračanica, Ričice, Sviće, Kopilo, Crkvice, and Radakovo.

The study area is large 7 (W-E) x 9 (S-N) km (Fig. 6) and is located in the central part of Bosnia and Herzegovina, which is limited with coordinates (Gauss Krueger zone 6) 6489.5 (W) - 6496.5 (E) and 4892.5 (S) - 4901.5 (N). Of the total 63 km2 of the study area, the urban area occupies 13.2 km2 (settlements: 9.5 km2 and industry zone 3.7 km2), cultivated land, meadows and pastures 31.5 km2, forests 17.2 km2 and surface water (the river Bosna, the Babina River, the Kočevo streams, etc) 1.1 km2. 23.2 km2 of researched area lies less than 400 m above sea level, in lowland where the city is developed.

The urban part of today's Zenica was formed during several specific periods which can chronologically be dated to the time of Neolithic community, Illyrian old towns’ ruins, Roman Municipium Bistua Nuova, Early Christian double Basilica, the medieval Bosnian Kingdom, the Ottoman Empire (1463 - 1878), Austro-Hungarian period (Fig. 4) and period after II WW (Fig. 5). In 1991, were registered 150,000 inhabitants, while town's population today is in excess of 170.000 (www.zenica.ba).

Climate in Zenica is temperate continental climate with warm summer and cold winter. Mean annual temperature is from 5-10oC, means temperature in January is between 1o and 2oC and in July 22-24oC. Means annual precipitations are about 1000 mm (http://www.fmzbih.co.ba/). Thermal inversion is frequent in Zenica basin, especially in winter months. If temperature inversion takes long time, contents of harmful substances increase in bottom of the basin and transport of substances goes on mostly in horizontal direction. There is a warm, light, and

23 clean air over temperature inversion. Phenomenon finishes when stronger wind starts blowing. However, quality of air in Zenica municipality is problematic, especially when ironworks have worked at full capacity. Zenica was the first city in Bosnia and Herzegovina who started with public monitoring of SOx and NOx emissions.

Figure 4: The town Zenica in Austro-Hungarian period (http://www.zenica.ba)

Figure 5: The town Zenica today (http://www.zenica.ba)

Figure 6: Generalized land use map of study area 3.2. GEOLOGICAL DESCRIPTION

The city of Zenica is resided in a valley that is covered with alluvium of the River Bosna, partly on alluvial terrace sediments. Geology of the study area is taken from Basic Geological Map, sheet Zenica, M 1: 100,000 (Fig. 7) (Živanović, 1975).

3.2.1. Mesozoic

The oldest rocks in study area are Jurassic ages. In the belt of Tithonian-Vallanginian beds of Zenica, series of flysch or Upper Vranduk series (2J,K) is isolated. The Upper Vranduk series is represented with marly limestones, calcarenites, detritic limestone with a rare nodules of hornfels, marls and sandy claystones. Depth of this series is about 600 m. Cretaceous beds are 3 mostly represented with Senonian flysch (K 2) that is developed as discontinue belt between Jurassic-Cretaceous flysch and Oligo-Miocene complex. Senonian flysch include a massive limestones and limestone breccias.

3.2.2. Cenozoic

3.2.2.1. Oligo - Miocene complex (Ol,M)

Based on lithology differences and paleontogy characteristics, the Oligo-Miocene polyfacial complex in the study area is divided into two lithostratigraphic units: • Basal zone (1OL,M) – appear next to the village Gračanica, near Zenica, represented by clay, sandy and marly sediments. In Gračanica this layer has a depth till 100 m. • Variagated series (3OL,M) - under main coal zone, “the Variegated series” is developed. In the mine area of Zenica, some coal layers are exploited. Lithology of the variegated series is represented by clastites and marles with coal beds in base.

Figure 7: Generalized geological map of study area 3.2.2.2. Older Miocene complex (M2,3)

Second cycles of sedimentation or older Miocene complex are separated into three lithostratigraphic units:

Principal coal zone (M1,2): By this name are understood layers of III lower coal zone. Within a framework of principal coal zone, a coal mines Drivuša, Raspotočje, Stara Jama and Podbrežje are situated. In the area of Zenica, the main coal zone is composed with four layers: • III lower coal zone, 5 m depth; grey chalky marls with Carpolithes valvatus, depth about 40 m • II lower coal zone Fossarulus tricarinatus, 4-12 m depth; clay marls (8 m depth) • I lower coal zone, 1.5 m depth; chalky marls, sanstones, clay marls and fine grained conglomerates with depth about 80 m • Principal coal zone 10 m depth

1 Roof limestone zone ( M2): After the Principal coal zone, this is the second economically important coal zone. Roof limestone zone is located 40 m under the Principal coal zone and is developed as a narrow belt in Drivuša, Mošćanica and Raspotočje. Limestones of this zone are relatively strong with high level of diagenesis. Colour is yellowish until white, partly porous or bituminous with numerous fossils (Limnaea, Gliptostrobus, Carpolithes feveatus).

Lašva zone (M2,3): In the Lašva series conglomerates are dominant bedrocks and alternate with layers of sandstones, marls and limestones. Total depth of the Lašva series is about 400- 800 m. Conglomerates are mostly limestone conglomerates, and material that forms those rocks is Mesozoic ages (Cretaceous flysch diabase-hornstone formation, etc). In the upper parts of the Lašva series, Triassic dolomites and Paleozoic pebbles are noticed. This series is very poor with fauna.

3.2.2.3. Quaternary (Q)

The youngest sediments are Holocene ages and are represented with upper terraces (t2), lower terraces (t1) and alluvium (a1). Younger Quaternary layers are developed along present watercourse or something higher in gravel-conglomerate terraces.

28 3.2.3. Tectonic

The town Zenica is situated in the Sarajevo-Zenica depression. Most important tectonic movements of Tertiary sediments happened in Miocene-Pliocene border and cause disruption of sedimentation in this part of terrain. In the Orlak syncline or the Zenica syncline, the youngest basin sediments of the Orlak’s conglomerates have remained. Apart this syncline, some others are determined as well. In the fold Lašva, along the one gentle anticline fold, the river Lašva has formed its river bed. In the study area, some radial disarrangement is found. One of the most significant fault, the Podbrežani fault, which is situated between Coal mines Stara Jama and Podbrežje in Zenica, is well known. Interruption between them is about 400 m in the area of the Starnjanska River, where its southern block is downcast. In the Raspotočje area, drilling and mines works more stepfault with downcast NE blocks have also found. These blocks have local marks “terraces” with numbers from I to VII. Exactly in those terraces in the pit Raspotočje, exploitation of coal performs until today. The faults have typical NW-SE longitudinal direction of providing. In the areas of Drivuša and Mošćanica, a few faults were found, but also in pits Stranjani and Stara Jama (Živanović, 1975).

3.3. PEDOLOGICAL DESCRIPTION

3.3.1. Automorphic soils

Automorphic soils are defined as well drained soils. Rendzinas are weakly developed, shallow soils that are formed on highly calcareous material mostly on dolomites and limestons. The Rendzinas constitute a simple A-C profile, dark calcareous topsoil immediately over shattered limestone. In the study area, Rendzinas and Cromic Cambisols are found in massive limestones and brecciac of the senonian Flysch, on limestones of clastic carbonate series and the Lašva series as well.

Ranker are very shallow soils, formed on steep slopes where erosion hinders further soil development. There developed over non-calcareous material. Rankers are called A-C soils, as the topsoil or A horizon is immidiatelly over C horizon (unaltered parent material). In the study area Eutric Rankers and Eutric Cambisols are found in Jurassic-Cretaceous marly limestones, calcarenites and detritic limestones of the Vranduk series, over clastites, marls,

29 conglomerates, sandstones and clays of Oligo-Miocene complex, but also on Quaternary terraces.

3.3.2. Hydromorphic soils

Hydromorphic soils are poorly drained and form because of the permanent or periodical presence of groundwater, precipitation, or floodwater in or on the soil profile.

Fluvisols are soils developed in alluvial deposits. These soils showing fluvic properties, having no diagnostic horizons other than an ochric, a mollic or an umbric A-horizon, or a histic H-horizon, and occur in periodically flooded areas, in alluvial plains and valleys, in climates ranging from arctic to equatorial and from semi-arid to perhumid. Fluvisols developed only on the youngest Quaternary material, alluvium.

3.3.3. Anthropogenic soils

Anthropogenic soils are the product of man's activities. They can be either automorphic or hydromorphic, depending on the level of a water table. Because of cultivation, the natural soil structure can be changed. Intense fertilization with organic fertilizers causes the formation of garden soils, which are common in Zenica and its surroundings.

3.4. HISTORY OF IRONWORKING IN ZENICA AREA

Construction of the iron and steelworks in Zenica started in 1892. In 1899, the iron and steelworks produced about 3.700 tons of rolled products. Steel making in open-heart furnaces was introduced in the first decade of the 20th century. Until 1911, three furnaces were built. The largest manufacturing 32.971 tones, in Austro-Hungarian period (Fig. 8) were in 1912. Between the I and the II World War, a stagnation of industrial production is registered.

Figure 8: The ironworks in Austro-Hungarian period (Photo by R. Šajn)

Through the period 1936-1940, the heavy section rolling mill; the new steel making plant; as well as the nail and drawn wire plant were constructed. In 1940, the iron and steel works produced 1/3 of the total production of steel and rolled production of Yugoslavia. Production of the iron and steelworks was not even stopped during the World War II.

From 1948-1958, Zenica and iron and steelworks were the biggest construction site in the former Yugoslavia. Production increased to 300.000 tons of the steel during that period.

Because of bigger and bigger demands for steel, in 1972 implementation of phase II of construction started for the purpose to reach the capacity of almost two million tons of steel per year. This construction phase was completed in 1978. By putting this facilities into the operation and expansion of production continued in 1986 and reached record of 1.72 million tons of pig iron and 1.91 million tons of crude steel. At the beginning of the war, in April 1992, due to break of the railway and road communication lines the continuous production was stopped. In 1998, emerged a new company called "BH Steel Company" which continued production but with less capacity. Finally, in December 2004, BH Steel Company joined to biggest multinational steel company, Mittal Steel, and has been renamed into the Mittal Steel Zenica (Fig. 9) (http://www.bhsteel.com.ba /istorija.htm).

Figure 9: The ironworks today (Photo by R. Šajn)

3.5. REWIEV OF PREVIOUS RESEARCH IN ZENICA AREA

Exploitation of pit and its processing in area of present Bosnia and Herzegovina is apparent from the earliest ages. However, significant develop of mining is noticed in the middle ages. Over 14th and 15th century, Pb, Cu and Ag mines were opened. At the end of 19th century, during Austro-Hungarian occupation, throughout Bosnia coalmines were opened. In the coalmines of Zenica (Raspotočje, Drivuša and Stara Jama) in 1880, coal exploitation has started. In 1892, iron and steel production has begun. According to growth in coal, iron and steel production (in 1990, 1.4 million tones of steel, 924.000 tones of coal), left important environmental pollution. Because of huge water, air and soil pollution, Zenica has always been interesting research area.

Previous researches have usually considered most common heavy metals such as Cd, Cu, Fe, Pb, Zn, and Hg. Unfortunately, huge amount of data is lost forever in last war (1992-1995). On of the latest research of heavy metals in soil shows high concentrations of Pb, Zn, Cu, Fe and S (Goletić, 2001). In part of his doctoral dissertation, the results are compared to results in 1989 (Tab. 3). The author has concluded that concentrations of those elements exceed

32 allowed values and the concentrations have decreased in period of 10 years because of the ironwork interruption.

Table 3: Concentrations of heavy metals in soil (Goletić, 2001)

Point Pb (mg/kg) Zn (mg/kg) Cu (mg/kg) Fe (%) S (mg/kg)

Year 1989* 1999 1989* 1999 1989* 1999 1989* 1999 1989* 1999 TE 263 97 215 303 65 43 6.85 5.04 600 769 PE 128 65 157 151 58 46 4.67 3.85 1300 571 GR 129 84 168 170 48 59 4.07 3.80 733 725 ST 75 46 106 112 39 40 4.67 3.46 267 274 JV 70 55 107 96 38 36 4.21 3.07 167 203 MU 80 68 123 130 52 42 5.04 3.48 267 227 AR 49 56 84 95 64 50 6.29 3.69 333 320 OR 57 45 93 91 85 61 3.24 2.78 300 249 SE 67 38 135 121 65 42 3.61 2.72 433 374

High concentrations of chalcophile and siderophile elements in the town Zenica have found. From 22 selected chemical elements, one natural and two anthropogenic groups were isolated (Alijagić & Šajn, 2006).

33 4. MATERIAL AND METHODS

4.1. SAMPLING DESIGN

Area of 52 km2 is covered with sampling grid especially settlement parts of the Zenica, the area of industrial activity (ironworks) and wider valley of the River Bosna. SW and NE, extremely parts of described area (Fig. 10) were not included in study area because were not interesting in this research work.

The entire area along valley was separated into cells by the sampling grid with a density of sample per km2. In the urban zone, the sampling density is increased in eight locations. In area of ironworks, the soil samples were not collected because it was not allowed by the ironworks owner, and sampling density increased in places were it was possible (out of border of ironworks).

Altogether, in 62 sampling points, 124 samples were collected. In 2004, near ironwork only two pilot samples of topsoil (0-5 cm) and two samples of attic dust were collected. In 2005, research is enlarged on 60 sampling points. In each sampling point were collected samples of topsoil (0-5 cm) and bottom soil (20-30 cm) (Fig. 11).

With regard to sample location, group of 19 sites represent the area with biggest expected influence on environment. Accordingly, there are isolated into particular group. Rest of samples were isolated into group where pollution has reduced.

In geological sense, 10 sites are located on the Quaternary Alluvium, 14 on Quaternary river terraces, 16 on the Miocene Oligocene clastites, 11 on the Cretaceous carbonate rocks and 11 on the Jurassic-Cretaceous flysch rocks (the Vranduk series).

Figure 10: Map of sampling locations with interpolated area 4.2. SAMPLING MATERIALS

4.2.1. Soil sampling

One sample represents the composite material collected at the central sample point itself and at six points within the radius of 50 m around it (Fig. 12). In the urban zone, within the town, urban soil, such as soil in the gardens and on grass verges was sampled. In each sampling point, topsoil (0-5 cm) and bottom soil (20-30 cm) are collected and the mass of such a composite was about 1 kg (Šajn, 2000; Šajn, 2003).

Priprava vzorcev A horizont

B B horizontbb B horizont

Figure 11: An example of soil profile (Photo by R. Šajn)

Figure 12: Soil sampling (Photo by R. Šajn)

Figure 13: Attic dust sampling (Photo by G. Žibret)

37 4.2.2. Attic dust sampling

Close to two sample locations of urban soil (0-5 cm) an old houses was chosen with intact attic carpentry. 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 (Fig. 13).

4.3. PREPARATION OF SAMPLES

All samples of soil and attic dust were air dried, then in fan drier at 40°C. The dry material has been gently crushed in the ceramic mortar and then the fraction smaller than 2 mm was pulverized (Darnley et al., 1995; Salminen et al., 1998). The dried samples of attic dust are passed through the sieves with 1 mm, 0.5 mm, 0.25 mm, and 0.125 mm openings. The size fraction of attic dust smaller than 0.125 mm was prepared for the chemical analyses by the sieving (Šajn, 2000; Šajn, 2003) (Fig. 14 and 15).

Figure 14: Preparation of samples (I) (Photo by R. Šajn)

Figure 15: Preparation of samples (II) (Photo by R. Šajn)

4.4. ANALYTICAL METHODS

4.4.1. Analysing of chemical elements (ICP-MS)

Inductively Coupled Plasma Mass Spectrometry (ICP-MS) is a very powerful tool for trace and ultra-trace elemental analysis. ICP-MS is rapidly becoming the technique of choice in many analytical laboratories for the accurate and precise measurements needed for today’s demanding applications. In ICP-MS, a plasma or gas consisting of ions, electrons, and neutral particles is formed from Argon gas. The plasma is used to atomize and ionize the elements in a sample. The resulting ions are then passed through a series of apertures (cones) into the high vacuum mass analyzer. The isotopes of the elements are identified by their mass-to-charge ratio (m/e) and the intensity of a specific peak in the mass spectrum is proportional to the amount of that isotope (element) in the original sample (http://web.missouri.edu/ ~umcreactorweb/pages/ac_icpms1.shtml).

39 All samples are analyzed in the laboratory ACME, Ltd. in Vancouver, Canada. 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 200°C).

4.4.2. Analysing of Mercury (ASS-CV)

A simple and robust method for the determination of Hg in environmental samples by slurry sampling cold vapour generation atomic absorption spectrometry is proposed. Hg was determined with cold vapour atomic absorption spectrometry AAS-CV after aqua regia digestion (mixture HCl, HNO3 and water at 95°C). The Hg cold vapour generated directly from the acidified sample slurry was conducted to quartz T tube, placed in the atomizer of the spectrometer.

By using the conventional calibration against aqueous standard solutions, excellent results were obtained when aqua regia plus hydrofluoric acid was used as the slurry medium. Simplicity, low cost and high efficiency are some of the qualities of the proposed method, making it adequate for routine analysis.

40 5. RESULTS

5.1 DATA MATRIX

All field observation, analytical data and measurements were introduced to the data matrix. For each observation, there are 63 variables: sample identification number, geographic coordinates, type of sampling and analysis, land use, lithologic and geologic characteristic, type and texture of soil, possible contamination and its source, determination of 42 analyzed elements.

5.2. RELIABILITY OF ANALYSES

All samples (n=124), replicates (n=8) and geologic standards (n=12) 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 for all samples. Because the samples were a part of bigger consignment, sensitivity, accuracy and precision of analysis are accepted (2005-2006).

5.2.1. Detection limit

The sensitivity in the sense of the lower limit of detection was adequate for 39 out of 42 determined chemical elements. The elements Au, Be, and S 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 or on detection limit of the analytical method (Tab. 4).

41 Table 4: Detection limits of analysed elements (ACME, 2005-2006).

Elements Detection limit

Hg 0.01 mg/kg Ag, Au, Bi, Cd, Cr, Cu, Hf, La, Li, Mo, Nb, Ni, Pb, Rb, Sb, Sn, Ta, Th, U, W, Y, Zr 0.1 mg/kg As, Ba, Be, Ce, Co, Mn, Sc, Sr, V, Zn 1.0 mg/kg Na, P, Ti 0,001 % Al, Ca, Fe, K, Mg 0.01 % S 0.1 %

5.2.2. Accuracy

Accuracy of the analytical method for the remaining 39 elements was estimated by calculation of the relative systematic error between the determined and recommended values of geological standards.

Geologic standard materials GXR-2 (analyzed 5 times) (http://www.geostandards.lanl.gov /MaterialsByNumber.htm), SRM-2709 (analyzed twice) (https://srmors.nist.gov/tables/ view_table.cfm?table=111-7.htm) and SO-4 (analyzed 5 times) (http://georem.mpch- mainz.gwdg.de/sample_query.asp) (Govindaraju, 1989; Epstein, 1990) were used for estimating accuracy.

Accuracy (A) of the analytical method for the remaining 39 elements was estimated by calculation of the absolute systematic error between the determined (Xa) and recommended values (Xp) of geological standards (Fig. 16) using equation:

xa - xb A = 100 [%] xp

Most of elements show, in the range of the actual samples, very low deviations. The means of elements in the standards generally differ by less than 30 % of the recommended values. Larger negative deviations were observed for Zr, Hf and Sn (Fig. 16) and they were removed from further statistical analysis.

42 Li 20

CuCd Zn P Hg V Ca MnFe Ti 0 Pb CoAlNaTh Sr BaCe AgK La ScMg U As TaRbSb -20 W Bi Cr NiMo Y Nb

Sn Accuracy (%) -40

-60 Hf Zr

-80

Figure 16: Accuracy of analysed chemical elements

5.2.3. Precision

Precision is a measure of repeatability of determining a parameter in the same sample regardless of deviation from the true value (Rose at al., 1979). Precision (P) was tested by relative differences between pairs of analytical determinations (x1, x2) (Fig: 17) of the same sample using equation:

2 x1 - x2 P = 100 [%] ( x1 + x2 )

Precision was additionally tested by Thompson-Howarth method (Analytical Methods Committee, 2000). The reliability of analytical procedures was considered adequate for using the determined elemental contents in further statistical analyses.

Most elements determined in standards differ on average, by less than 15 % from their recommended values (Fig. 17).

43 15

10 Precision (%) Precision 5

0 P U V K Y Sr Ti Zr W Li Hf Cr Bi Ni Al Fe Sc La Sb Ta Sn Pb As Ba Ca Zn Na Th Ce Rb Hg Ag Cd Nb Cu Co Mo Mg Mn Elemets

Figure 17: Precision of analysed chemical elements

The reliability of analytical procedures was considered adequate for using the determined elemental contents in further statistical analyses.

5.3. DATA PROCESSING

Data analysis and production of maps were performed on a PC using the Paradox (ver 11), ArcInfo (ver. 9.1), Statistica (ver. 6.1), Autocad (ver. 2005) and Surfer (ver. 8.0) software.

5.3.1. Statistical methods

5.3.1.1 Basic statistics and normality of distribution

For the data, the methods of parametric and nonparametric statistics were used. Normality of data distributions were tested (Snedecor & Cochrane, 1967).

44 Table 5: Basic statistics of the chemical elements in topsoil (0-5 cm); n =60.

Dis Min Max X, Xg Me A E

Al N 1.3 8.1 5.8 6.1 -1.29 3.16 Ca Log 0.46 26 2.7 2.5 0.30 -0.99 Fe N 1.4 6.1 4.1 4.2 -0.85 2.02 K N 0.17 2.1 1.3 1.2 -0.46 2.64 Mg Log 0.31 1.7 0.78 0.77 -0.24 0.40 Na N 0.019 0.91 0.40 0.39 0.36 -0.26 P Log 0.036 0.17 0.078 0.076 0.49 0.46 Ti N 0.059 0.43 0.32 0.32 -0.99 2.08

Ag Log 0.10 2.1 0.72 0.70 -0.56 0.45 As Log 11 117 32 33 -0.07 0.83 Ba Log 90 1877 522 470 0.22 0.71 Bi N 0.10 1.3 0.55 0.50 0.77 1.85 Cd Log 0.30 1.8 0.78 0.80 -0.14 -0.19 Ce N 8.0 82 56 57 -0.84 2.06 Co N 5.0 37 22 21 0.13 0.32 Cr Log 34 555 156 155 -0.49 3.79 Cu N 11 92 53 49 0.25 0.25 La N 4.5 44 29 29 -0.80 2.42 Li N 7.4 73 48 48 -0.59 1.57 Mn Log 652 3090 1424 1390 0.14 -0.26 Mo Log 0.30 1.9 0.77 0.75 -0.18 -0.13 Nb N 1.4 11 6.7 6.5 -0.18 0.50 Ni Log 47 329 122 126 0.01 -0.34 Pb Log 19 384 122 113 -0.36 0.43 Rb N 18 119 83 83 -0.64 1.66 Sb Log 0.70 16 5.1 5.5 -0.57 0.48 Sc N 2.0 15 11 12 -1.34 3.23 Sr Log 47 395 109 102 0.77 0.82 Ta N 0.10 0.70 0.47 0.50 -0.32 0.78 Th N 2.1 14 9.2 9.4 -0.57 1.83 U Log 0.70 3.6 1.7 1.7 -0.63 4.66 V N 18 135 98 99 -0.96 2.23 W N 0.30 1.9 1.2 1.2 -0.66 1.73 Y N 3.7 27 18 18 -0.52 1.06 Zn Log 46 474 202 188 -0.25 1.06

Hg Log 53 2973 222 188 0.72 1.69

Dis – distribution (N – normal, Log - log-normal); X – mean; Xg - geometric mean; Me - median, Min – minimum; Max – maximum; A – skewness; E - kurtosis. Average values of Al, Ca, Fe K, Mg, Na, P and Ti are in %, Hg in µg/kg and remaining elements in mg/kg.

45 Table 6: Basic statistics of the chemical elements in bottom soil (20-30 cm); n=60.

Por Min Max X, Xg Me A E

Al N 1.3 8.4 6.1 6.3 -1.20 2.81 Ca Log 0.28 26 2.8 2.9 0.03 -0.98 Fe N 1.5 6.0 4.2 4.3 -0.86 1.33 K N 0.17 1.9 1.3 1.3 -0.88 2.72 Mg Log 0.31 1.8 0.79 0.78 -0.12 0.74 Na N 0.019 0.90 0.42 0.40 0.42 -0.29 P Log 0.029 0.16 0.061 0.058 0.49 0.16 Ti N 0.059 0.42 0.30 0.31 -0.74 0.79

Ag Log 0.10 2.2 0.41 0.50 -0.15 -0.68 As Log 10 142 33 34 -0.09 1.41 Ba Log 101 2279 511 427 0.61 0.34 Bi N 0.10 1.1 0.49 0.40 0.99 1.91 Cd Log 0.20 2.1 0.58 0.60 -0.19 -0.19 Ce N 8.0 88 59 59 -0.77 1.57 Co N 6.1 42 24 23 0.19 0.15 Cr Log 32 740 180 182 -0.67 3.46 Cu N 12 99 52 49 0.41 0.44 La N 4.6 47 30 31 -0.78 1.96 Li N 8.5 85 51 50 -0.28 1.36 Mn Log 632 3424 1453 1479 0.05 -0.30 Mo Log 0.30 1.9 0.78 0.80 -0.38 0.41 Nb N 1.5 13 7.1 6.9 0.32 0.97 Ni Log 51 338 131 135 -0.06 -0.27 Pb Log 14 488 87 82 0.05 0.23 Rb N 16 129 81 82 -0.33 1.44 Sb Log 0.80 21 4.3 4.0 -0.07 -0.09 Sc N 2.0 16 12 13 -1.18 2.42 Sr Log 48 381 116 113 0.69 0.67 Ta N 0.10 0.90 0.57 0.60 -0.22 0.73 Th N 1.9 15 9.6 9.8 -0.85 1.97 U Log 0.60 2.4 1.7 1.7 -2.15 9.43 V N 5.0 138 97 98 -1.00 1.71 W N 0.30 4.2 1.2 1.1 3.82 2.31 Y N 3.4 27 18 18 -0.44 0.90 Zn Log 36 555 167 167 -0.10 1.08

Hg Log 58 959 157 129 0.69 -0.55

46 On the basis of the results of normality tests and visual inspection of distribution histograms for 36 elements in topsoil (0-5 cm) and bottom soil (20-30 cm) the normality was assumed for natural values of Al, Fe, K, Na, Ti, Bi, Ce, Co, Cu, La, Li, Nb, Rb, Sc, Ta, Th, V, W and Y. For the other elements (Ca, Mg, P, Ag, As, Ba, Cd, Cr, Mn, Mo, Ni, Pb, Sb, Sr, U, Zn and Hg) logarithms of contents were considered normally distributed.

Tabs 5 and 6 are showing estimation of basic statistic parameters of 36 chemical elements in topsoil and bottom soil. In tables, the symbol “Dis” presents distribution, which is normal (N) or log-normal (Log), ˝X or Xg˝ mean or geometric mean, ˝Me˝ presents estimate values of median, ˝Min˝ in ˝Max˝ minimum and maximum concentration of elements in sample, ˝A˝ skewness and ˝E˝ kurtosis on treated region.

5.3.1.2. Bivariate statistics (correlations)

The degree of association of chemical elements in attic dust and soil was assessed with the linear coefficient of correlation r (Le Maitre, 1982) between their contents in the samples. It was qualitatively assumed that the absolute values of r between 0.3 and 0.7 indicate good association, and those between 0.7 and 1.0 strong association between elements.

Table 7a: Matrix of correlation coefficients (r) of selected 14 chemical elements – First group (n=120)

Ca -0.67 K 0.83 -0.50 Ti 0.76 -0.84 0.56 Ce 0.75 -0.72 0.69 0.71 La 0.74 -0.68 0.67 0.70 0.98 Li 0.83 -0.63 0.55 0.75 0.55 0.55 Nb 0.74 -0.80 0.53 0.83 0.80 0.81 0.65 Rb 0.90 -0.61 0.86 0.66 0.78 0.75 0.67 0.68 Sc 0.91 -0.66 0.67 0.79 0.58 0.59 0.87 0.66 0.75 Ta 0.73 -0.74 0.54 0.73 0.80 0.80 0.65 0.89 0.64 0.63 Th 0.78 -0.70 0.72 0.69 0.97 0.97 0.57 0.82 0.80 0.60 0.80 V 0.91 -0.68 0.69 0.84 0.63 0.64 0.85 0.73 0.78 0.93 0.66 0.64 Y 0.81 -0.61 0.54 0.75 0.69 0.72 0.78 0.73 0.73 0.83 0.67 0.68 0.86

Al Ca K Ti Ce La Li Nb Rb Sc Ta Th V

47 Table 7b: Matrix of correlation coefficients (r) of selected 5 chemical elements – Second group (n=120)

Na 0.65 Co 0.32 0.29 Cr 0.48 0.33 0.71 Ni 0.56 0.27 0.77 0.85

Mg Na Co Cr

Table 7c: Matrix of correlation coefficients (r) of selected 9 chemical elements – Third group (n=120)

Ba 0.71 Bi 0.74 0.62 Cd 0.83 0.66 0.74 Cu 0.55 0.65 0.61 0.60 Mo 0.54 0.50 0.57 0.60 0.41 Pb 0.92 0.78 0.82 0.89 0.69 0.62 Sb 0.80 0.82 0.71 0.79 0.61 0.66 0.88 Zn 0.85 0.82 0.80 0.87 0.78 0.65 0.93 0.86 Hg 0.79 0.78 0.64 0.69 0.59 0.46 0.82 0.79 0.80

Ag Ba Bi Cd Cu Mo Pb Sb Zn

Because of better clearness, matrix of correlation coefficient is divided into three parts (Tabs. 7a, 7b and 7c) according to results of multivariate analysis (chapter 5.3.1.3).

5.3.1.3. The multivariate statistical method

The multivariate cluster analysis and R-mode factor analysis (Kosmelj, 1983; Davis, 1986; Rodionov et al., 1987; Reimann et al., 2002) were used to reveal the associations of chemical elements.

Cluster analysis is not one method, but type of proceedings, that is used to arrange a set of cases into clusters. The aim is to establish a set of clusters such that cases within a cluster are more similar to each other than they are to cases in other clusters (Rodionov et al., 1987). Known is more cluster techniques, which are based on agglomeration more elements

48 according to their composition, giving different results. Hierarchical clustering is chosen based on correlation coefficient (r).

Result of cluster analysis is showed in form of dendogram (Fig. 18). 8 chemical elements (As, Ba, Fe, Mn, P, Sr, U and W) were eliminated from further analysis because of tendency of forming their own clusters and are not showing reasonable connection with remained chemical elements.

Al Sc V Li Y Ti Ce La Th Nb Ta K Rb Mg Na Co Cr

Chemical elements Ni Ag Cd Pb Zn Bi Sb Hg Cu Mo

020406080100 Linkage distance (%)

Figure 18: Tree diagram of cluster analysis (n=120, 28 selected elements)

Dendrogram of cluster analyze (Fig. 18) are giving results for the 28 remaining chemical elements and their mutual connecting to three groups. The chemical elements that belong to the first group (Al, Ca, Ce, K, La, Li, Nb, Rb, Sc, Ta, Ti Th, V and Y) are linked on the level

49 85% with the group (Co, Cr, Na, Ni and Mg). The anthropogenic chemical elements Ag, Bi, Cd, Cu, Hg, Mo, Pb, Sb and Zn on the level 100% join to them.

Table 8: Matrix of dominant rotated factor loadings (n=120, 28 selected elements)

F1 F2 F3 Comm

Th 0.93 91.4 Ce 0.93 88.9 La 0.92 89.1 Nb 0.90 84.1 Al 0.89 86.8 Rb 0.88 78.3 Ta 0.84 75.4 Y 0.82 77.6 V 0.78 83.1 K 0.77 59.7 Ti 0.71 79.7 Sc 0.71 89.6 Li 0.67 73.3 Ca -0.71 69.9

Pb 0.97 96.0 Zn 0.95 96.9 Sb 0.94 89.1 Cd 0.93 86.8 Ag 0.93 86.8 Bi 0.91 84.9 Hg 0.88 84.1 Mo 0.73 60.2 Cu 0.66 75.9

Ni 0.89 80.5 Co 0.78 79.2 Cr 0.76 60.9 Mg 0.75 59.5 Na 0.70 52.4

Var 35.1 26.1 18.1 79.3

F1, F2, F-3 - Factor loadings Com - Communality in % Var - Variance in %

Factor analysis (FA) derives from numerous variables a smaller number of new, synthetic variables called factors (Le Maitre, 1982). The factors contain a large part information of

50 original variables, and they may have certain meanings. The factor analysis was performed on variables standardized to zero mean and unit of standard deviation (Reimann et al., 2002). As a measure of similarity between variables, the product-moment correlation coefficient (r) was applied. For orthogonal rotation, the varimax method was used.

In the factor analysis, 120 samples of the topsoil and bottom soil were considered. Same as in the cluster analysis, also in the factor analysis 28 chemical elements were considered. From the multivariate analysis, the chemical elements As, Ba, Fe, Mn, P, Sr, U and W were eliminated from a further analysis because they have low share of communality or tendency to form independent factors. With the factor analysis distribution is decreased on three synthetic variables (F1 to F3), have connected regard to geochemical similarities, which are include 79% of variability of treated elements (Tab. 8).

Factor 1 (F1) is strongest and represent 35 % of entire variability of remaining elements. The F1 associate the high concentration of Al, Ce, K, La, Li, Nb, Rb, Sc, Ta, Ti Th, V and Y, but also the low concentration of Ca, -0.71. The group represents chemical elements that are the most probably naturally distributed (Tab. 8). Factor 2 (F2) is the second strongest factor and include 26% of entire variability. This factor principally associates the heavy metals such as Ag, Bi, Cd, Cu, Hg, Mo, Pb, Sb and Zn which have anthropogenic origin (Tab. 8). In the factor 3 (F3) are associate elements Co, Cr, Na, Ni and Mg, that include 18 % of entire variability. The group also represents elements that are the most probably naturally distributed (Tab. 8).

5.3.1.4. Enrichment ratio

The enrichment ratio (ER), defined as the ratio of grade of a metal element in a deposit to the crustal abundance of the metal, is proposed for assessing mineral resources. According to the definition, the enrichment ratio of a polymetallic deposit is given as a sum of enrichment ratios of all metals (http://www.springerlink.com/content/kq072l25077826p6/).

The enrichment ratio provides a much better measure for comparison. This ratio has been calculated by dividing the concentrations in attic dust by the topsoil (Fig. 19) and topsoil by bottom soil (Fig. 20) for a given site.

51 In the figures 19 and 20, is given enrichment ratio of the 28 selected elements, according to the results of cluster and factor analyses. Where the ratio of attic dust/topsoil (Fig. 19) is lower than 1, the values are higher in the topsoil otherwise are higher in the attic dust. The same shall apply to ratio topsoil/bottom soil (Fig. 20). Values of ER higher than 1, indicate enrichment in the topsoil. On the both figures is visible mainly large enrichment of heavy metals in attic dust vs. topsoil and topsoil vs. bottom soil.

Third group 4

3 (topsoill) / C

2 (attic dust) (attic

Enrichment ratio Second group C

1 First group

0 K Y V Ti Li Al Sc Cr Ni Bi La Ta Pb Sb Ce Th Ca Na Zn Rb Nb Co Cu Cd Hg Ag Mg Mo Chemical elements Figure 19: Enrichment ratios: attic dust versus topsoil (0-5 cm) – 28 selected elements

52 1.8

1.6

Third group 1.4 (bottom soill) (bottom

/ C 1.2 Enrichment ratio (topsoil) C First group Second group 1.0

0.8 Y K V Li Ti Sc Al Cr Ni Bi Ta La Sb Pb Ce Th Ca Na Zn Nb Rb Co Cu Cd Hg Ag Mg Mo Chemical elements

Figure 20: Enrichment ratios: topsoil (0-5) versus bottom soil (20-30 cm) – 28 selected elements

5.3.1.5. Map of areal element distributions

The universal kriging with linear variogram interpolation method (Perišić, 1983; Davis, 1986) was applied to construct the maps of areal distribution of particular elements and factor values in topsoil and bottom soil. The basic grid cell size for interpolation was 100 x 100 m. For class limits, the percentile values of distribution of the interpolated values were chosen. Seven classes of the following percentile values were selected: 0-10, 25-40, 40-60, 60-75, 75-90, and 90-100.

53 6. DISCUSSION

Two geogenic and one anthropogenic geochemical association were established on the basis of: visually indicated similarity of geographic distribution of elemental patterns in topsoil and bottom soil; comparisons of the basic statistics (Tabs. 5 and 6); the correlation coefficient matrices (Tabs. 7a, 7b and 7c); the results of cluster (Fig. 18) and the factor analyses (Tab. 8) and comparisons of the enrichment ratios attic dust vs. topsoil and topsoil vs. bottom soil (Figs. 19 and 20).

6.1. NATURAL DISTRIBUTION OF CHEMICAL ELEMENTS

The first group consists the elements Al, Ca, Ce, K, La, Li, Nb, Rb, Sc, Ta, Ti Th, V and Y. Those elements are only a little affected by anthropogenic activities. Characteristic for the group are high values of the correlation coefficients between chemical elements (Tab. 7a). The existence of the group is confirmed also by the results of cluster (Fig. 18) and the factor analysis (Tab. 8). The strongest Factor 1 contains high values of Al, Ce, K, La, Li, Nb, Rb, Sc, Ta, Ti Th, V and Y, and low value of Ca, explaining 35% of total variability within the data (the 28 selected chemical elements).

For all these elements characteristic is their c. 75% depletion in the attic dust with respect to the topsoil (Fig. 19). In addition, it is important minute depletion of the mentioned elements in the topsoil with respect to the bottom soil (Fig. 20).

Clearer ratios are obtained comparing the enrichment factors of groups with a different geological background (Fig. 21). Compared are the enrichments between the topsoil and the bottom soil areas of the Older Miocene clastites series and the Quaternary alluvium (the sign M,Q – group of the 26 locations); areas of the Senonian limestones and limestone breccias (the sign Ca – group of 11 location) and a different rocks (the sign Rest – group of the 23 location). High concentrations and the enrichments of mentioned elements in bottom soil, exactly on carbonate rock is noticeable (Fig. 21).

54 2.0

1.8

M,Qcm) (0-5 1.6 /C

1.4

Enrichment ratio Enrichment Ca (bottom soil) 1.2 group of samples) group of Ca (topsoil)

C Rest (bottom soil) Rest (topsoil) 1.0 a e M ,Q (bottom soil) r a b i A T N L a L Y e M,Q (topsoil) C V h T l c A S b i R T K Elements

Figure 21: Enrichment ratios of the first group of chemical elements according to lithology

M,Q - M2,3 series and Q alluvium (group of the 26 sampling locations) 3 Ca - K2 limestones and limestone breccias – (group of the 11 sampling locations) Rest - Other lithology units (group of the 23 sampling locations)

Their sources are mainly a natural phenomena, such as a rock weathering and a chemical processes in soil. In addition, the areal distribution of Factor 1, scores (Al, Ce, K, La, Li, Nb, Rb, Sc, Ta, Ti Th, V, Y and - Ca) in the both soil horizons is closely dependent on the 3 lithology. Their highest contents, were found in areas of the Senonian (K2 ) limestones and the limestone breccias and on particular areas of the outcropping carbonate rocks on the

Oligo-Miocene (Ol,M) clastite and marl complex. The Older Miocene (M2,3) clastic-carbonate series (Fig.7) and their lowest values in areas of the outcropping clastites of the Older

Miocene (M2,3) clastic-carbonate series and (Q) Quaternary alluvium, that was formed as a product of weathering mentioned rocks. The areal distribution of these elements in the two sampling materials is highly similar. The Factor 1 scores distribution is shown in Figure 23.

The second group consists the elements Co, Cr, Na, Ni and Mg. Those elements are also a little affected by anthropogenic activities like the first group. Characteristic for the group are relative high values of the correlation coefficients between the chemical elements (Tab. 7b). The existence of the group is confirmed also by results of the cluster (Fig. 18) and the factor

55 analysis (Tab. 8). The Factor 3 contains high values of Co, Cr, Na, Ni and Mg explaining c. 18% of total variability within the data (the 28 selected chemical elements).

Characteristic for all these elements is nearly same to content in the attic dust with respect to the topsoil (Fig. 19). Similarly to the first group of elements, also for this group of elements is significant minor depletion with the mentioned elements in the topsoil with respect to the bottom soil (Fig. 20).

In this group of elements are compared the enrichments between topsoil and bottom soil on areas of the Older Miocene clastites series and the Quaternary alluvium (the sign M,Q – group of the 26 locations); areas of the Jurassic-Cretaceous flysch rocks – the Vranduk series (the sign Fl – group of the 11 locations) and on a different rocks (the sign Rest – group of the 23 samples). The high concentrations, and also the enrichment of the mentioned elements in bottom soil, exactly on the Jurassic-Cretaceous flysch rocks – the Vranduk series are noticeable (Fig. 22).

2.2

1.9 M,Q (0-5 cm) Fl (bottom soil) /C

1.6 Fl (topsoil)

Rest (bottom soil) 1.3

Enrichment ratio Enrichment Rest (topsoil) a e r

groupsamples) of A M,Q (bottom soil) C 1.0 M,Q (topsoil) a T b i N L a L Y Elements

Figure 22: Enrichment ratios of the second group of chemical elements according to lithology

M,Q - M2,3 series and Q alluvium (group of the 26 sampling locations) Fl - J,K flysch rocks - Vranduk series (group of the 11 sampling locations) Rest - Other lithology units (group of the 23 sampling locations)

Figure 23: Spatial Factor 1 scores (Al, Ce, K, La, Li, Nb, Rb, Sc, Ta, Ti, Th, V, Y and -Ca) distribution in the topsoil (above) and the bottom soil (below)

Figure 24: Spatial Factor 3 scores (Co, Cr, Na, Ni and Mg) distribution in the topsoil (above) and the bottom soil (below)

58 Similarly to the example of distribution of Factor 1 scores, the spatial distribution of Factor 3 scores (Co, Cr, Na, Ni and Mg) in the both soil horizons is closely dependent on the lithology. Their highest contents were found in areas of the Jurassic-Cretaceous (JK) flysch rocks – the

Vranduk series and their lowest values in areas of the Older Miocene clastites (M2,3),the clastic-carbonate series and the Quaternary (Q) alluvium. The Factor 3 scores distribution is shown in Figure 24.

6.2. ANTHROPOGENIC DISTRIBUTION OF CHEMICAL ELEMENTS

The group comprises Ag, Bi, Cd, Cu, Hg, Mo, Pb, Sb and Zn, chemical elements that were introduced into the environment through anthropogenic activities. Typical are their relatively high correlation coefficients (Tab. 7c). The group’s existence is confirmed also by results of multivariate statistical analyses (Fig. 18 and Tab. 8). The geochemical association is indicated by the second strongest Factor 2. It explains 26% of the total variability.

4.0

3.5

3.0 Rest (0-5cm) /C 2.5

2.0 Enrichment ratio Enrichment

group of samples) group of 1.5 Iron. (bottom soil) C Iron. (topsoil) 1.0 Surr. (bottom soil) a e g r A g b H P b Surr. (top soil) A S d a C B n i Z B u C o Elements M

Figure 25: Enrichment ratios of the second group of chemical elements according to land use Iron. - Ironworks and urban zone (group of the 17 sampling locations) Surr. - Surrounding (group of the 43 sampling locations)

Figure 26: Spatial Factor 2 scores (Ag, Ba, Bi, Cd, Cu, Hg, Mo, Pb, Sb and Zn) distribution in the topsoil (above) and the bottom soil (below)

60 Typical for this elemental assemblage is the enrichment of the elements in attic dust versus topsoil, from 2.2-times for the Cu to 4.9-times for the Sb (Fig. 19). The concentrations of mentioned elements in topsoil globally exceed the concentration in bottom soil from the Cu which has the same value in topsoil and bottom soil to 2.1-times for the Ag (Fig. 20).

For this group of elements are compared the enrichments between the topsoil and bottom soil on area of denser sampling grid (ironworks and urban zone – group of 17 locations) and also in surrounding (group of 43 locations). High concentrations and as well the enrichments of mentioned elements in topsoil is noticeable close to ironworks and urban zone (Fig. 25).

The spatial distribution patterns of individual elements do not differ much. In the both soil horizons a clear anomaly occurs among the river Bosna, the ironworks Zenica and also in the town centre. The shape of the dispersion halo has been strongly influenced by local winds and the shape of the Zenica basin. In spatial distribution, anomalies are more noticeable in topsoil than in bottom soil. Factor 2 scores distribution is shown in Figure 26.

61 6.3. DISTRIBUTION OF PARTICULAR HEAVY METALS IN SOIL

6.3.1 Arsenic (As)

Arsenic is the metal in a 15th group of periodic table with atomic number 33. In nature occurs usually in form of sulphides such as arsenopyrite FeAsS, realgare AS4S4, orpigment AS2S3 (Filipović & Lipanović, 1995). Anthropogenic sources of As are mining, metallurgic activities, and burning of fossil fuels that are main pollutants of air, water and soil (Gosar & Šajn, 2005). Large exposure or ingestion of As, can cause problems of digestive, nervous system and activity of heart (WHO, 2001).

Clarke in soil is 5 mg/kg (Rösler & Lange, 1972). As average in topsoil for the all study area amount to 32 mg/kg in range 11 - 177 mg/kg and for bottom soil 33 mg/kg in range 10 - 142 mg/kg (Tabs. 5 and 6). For As is important that there is not large difference in concentration between the topsoil and bottom soil. In the attic dust As average amount to 121 mg/kg. As average of attic dust exceed As average of surroundings samples of topsoil, more than twice, which explain its anthropogenic nature.

The highest concentrations of As in both soil horizons is found on NW part of study area in periphery, close to Tetovo coal zone. Slightly high concentrations are in surrounding of ironworks Zenica (Fig. 27). On mentioned area (17 locations around ironworks) As average in the topsoil amount to 40 mg/kg and in the bottom soil 41 mg/kg, what exceed estimated concentration of the surrounding (43 locations) about 40%. In settlement Graja, the maximal concentration for the topsoil is 117 mg/kg and bottom soil 142 mg/kg. Only in one more location N. Tetovo, which is close to previous one are found high concentration for As, 100 mg/kg in topsoil and 115 mg/kg in bottom soil.

Consequences of mining activities in areas of Pridražići, Jakovići and N. Tetovo represent main source of As, but less from ironworks activity (Fig. 27). As pollution of research area is significantly, concentration of As exceed Limit value in approximately 46 km2 in both soil horizons. Warning value is exceeded in about 32 km2 and critical in 2.2 km2 (Fig. 28).

Figure 27: Spatial arsenic distribution in topsoil (above) and bottom soil (below)

Figure 28: Spatial arsenic pollution in topsoil (above) and bottom soil (below) according to the Slovenian legislation (Ur. List RS 68/96)

64 6.3.2. Cadmium (Cd)

Cadmium is a relatively rare, soft, bluish-white, transition metal in the 12th group of the periodic table together with Hg and Zn. Main sources of Cd are sulfide ores galenite (PbS) and sphalerite (ZnS), where occur in small quantities. Ni is used in Ni-Cd battery production, alloy, galvanization processes, and pigments for example for plastic products (Dunnick & Fowler, 1987). Cd goes over to atmosphere mostly from colour metallurgy, ironworks, and steelworks, but also at processes of burning of fossil fuels. Cd concentration in soil more and more increase and already in many places exceed natural limit 1 mg/kg (Greenwood, 1984). Cd is used largely in batteries and pigments, for example for plastic products. Inhalation of cadmium-containing fumes can result initially in metal fume fever but may progress to death (http://www.en.wikipedia.org /wiki/Cadmium).

Clarke Cd in soil is 0.35 mg/kg (Bowen, 1979). Cd average in the topsoil amount to 0.78 mg/kg in range 0.3 – 1.8 mg/kg and for the bottom soil (20-30 cm) 0.58 mg/kg in range 0.2 – 2.1 mg/kg (Tabs. 5 and 6). For the Cd concentrations, differences between the topsoil and bottom soil are significant. Cd average of topsoil exceeds estimated Cd average of bottom soil for about 35 % (Fig. 20). Cd average of attic dust (4.3 mg/kg) exceeds estimated Cd average of the surroundings samples of the topsoil, almost three times (Fig. 19), which explain its anthropogenic nature.

The highest concentrations of Cd in both soil horizons are found closer to ironworks Zenica (Figs. 26 and 29). In the mentioned region (17 locations around ironworks) amount to average Cd in the topsoil 1.1 mg/kg and bottom soil 1.0 mg/kg, what exceed estimated concentration of surrounding (0.67 mg/kg – topsoil and 0.47 mg/kg – bottom soil) about twice (Fig. 26). Maximal values are found in the urban zone, around the ironworks and surrounding settlements in NW of the study area (Podbrežje, Podnožje, T. Brdo, Pridražići etc.) (Fig. 29).

The main source of Cd is consequence of ironworks activity. Cd pollution of the study area is inconsiderable (Ur. list RS 68/96 – Tab. 2). Concentrations of Cd exceed Limit value in approximately 11 km2 in topsoil and 7 km2 in bottom soil. Concentrations of Cd are not exceeding warning value in the study are (Fig. 30).

Figure 29: Spatial cadmium distribution in topsoil (above) and bottom soil (below)

Figure 30: Spatial cadmium pollution in topsoil (above) and bottom soil (below) according to the Slovenian legislation (Ur. List RS 68/96)

67 6.3.3. Cobalt (Co)

Cobalt is a hard, lustrous, silver grey metal, with atomic number 27, in 9th group of periodic table. It is found in various ores but usually not mined alone, and tends to be produced as a byproduct in Ni and Cu mining activities. The main ores of Co are cobaltite, erythite, glaucodot, and skutterudite. Co in small amounts is essential to many living organism, including humans. Co is a central component of the vitamin B-12 (Filipović & Lipanović, 1995).

Clarke of Co in soil is 8 mg/kg (Rösler & Lange, 1972). Co average in the topsoil amount to 22 mg/kg in range 5.0 – 37 mg/kg and for the bottom soil 24 mg/kg in range 6.1 – 42 mg/kg (Tabs. 5 and 6). Average of Co (19 mg/kg) in the attic dust is higher than average of the surroundings samples of the topsoil about 20%. There is no certain difference between the concentration of Co in the attic dust, topsoil and bottom soil (Figs. 19 and 20), therefore we can say that its distribution is natural conditional principally.

The lowest concentration of Co (19 mg/kg – topsoil and 20 mg/kg – bottom soil) are found on area of outcrops of the Miocene clastites and the Quaternary Alluvium, and the highest concentration of Co on the Jurassic-Cretaceous flysch rocks – the Vranduk series (30 mg/kg – topsoil and 33 mg/kg – bottom soil) (Figs. 24 and 31). Concentrations of Co are increased with depth, what claim the theory about the natural distribution of Co.

Regard to the Slovenian legislation (Ur. list RS 68/96 – Tab. 2) concentrations of Co exceeds limit values about 34 km2 in topsoil and 42 km2 in bottom soil (Fig. 32). Previously mentioned values are result of natural origin and on its anthropogenic activity, there is no largest influence.

Figure 31: Spatial cobalt distribution in topsoil (above) and bottom soil (below)

Figure 32: Spatial cobalt pollution in topsoil (above) and bottom soil (below) according to the Slovenian legislation (Ur. List RS 68/96)

70 6.3.4. Chromium (Cr)

Chromium is a steel grey, lustrous, hard metal, in the 12th group periodic table with atomic number 24. Cr is mined as chromite (FeCr2O4) ore. Though native Cr deposits are rare, some native Cr metal has been discovered (Filipović & Lipanović, 1995). Cr metal and Cr (III) compounds are not usually considered health hazard, but Cr (VI) compounds can be toxic if orally ingested or inhaled, and are irritating to eyes, skin and mucous membranes. WHO recommended maximum allowable concentration in drinking water for Cr (VI) is 0.05 mg/l (http://www.en.wikipedia.org/ wiki/Chromium).

Clarke of Cr in soil is 200 mg/kg (Rösler & Lange, 1972). Cr average in the topsoil amount to 156 mg/kg in range 34 – 156 mg/kg and for the bottom soil 180 mg/kg in range 32 – 740 mg/kg (Tabs. 5 and 6). Concentrations of the Cr in bottom soil exceed concentrations in topsoil about 15 % (Fig. 20). In the attic dust average Cr amount to 156 mg/kg what is similar to the Cr average in the surrounding samples of topsoil (Fig. 19). Also for the Cr distribution, it is possible to say that its distribution is conditional naturally.

Similarly to the Co, the lowest average of Cr (155 mg/kg – topsoil and bottom soil) we have found on areas of outcrops the Miocene clastites and the Quaternary Alluvium and the highest Cr average on the Jurassic-Cretaceous flysch – the Vranduk series (197 mg/kg – topsoil and 243 mg/kg – bottom soil) (Figs 24 and 33). Concentrations of the Cr that increase with depth significantly, especially on the Vranduk series, again claim our theory about natural distribution of Cr.

According to the Slovenian legislation (Ur. list RS 68/96 –Tab. 2) natural distribution of the Cr is significant. Concentrations of Cr exceed the Limit value about 49 km2 in both soil horizons (Fig. 34). Warning values exceed on 30 km2 in topsoil and in about 37 km2 in bottom soil and the critical value on 1.1 km2 in bottom soil of the study area (Fig. 34).

Figure 33: Spatial chromium distribution in topsoil (above) and bottom soil (below)

Figure 34: Spatial chromium pollution in topsoil (above) and bottom soil (below) according to the Slovenian legislation (Ur. List RS 68/96)

73 6.3.5. Copper (Cu)

Copper is a chemical element that has the symbol Cu, atomic number 29 and atomic mass 63.54. Cu can be found as native copper in mineral form. Minerals such as the sulfides: chalcopyrite (CuFeS2), bornite (Cu5FeS4), covellite (CuS), chalcocite (Cu2S) are sources of

Cu, as are the carbonates: azurite (Cu3(CO3)2(OH)2) and malachite (Cu2CO3(OH)2) and the oxide: cuprite (Cu2O). Common oxidation states of Cu include the less stable Cu (I) and the more stable Cu (II), which forms blue or blue-green salts and solutions (Filipović & Lipanović, 1995). Cu is essential in all higher plants and animals. When Cu is first absorbed in the gut it is transported to the liver bound to albumin. Cu is found in a variety of enzymes. In addition to its enzymatic roles, Cu is used for biological electron transport. It is a ductile metal with excellent electrical conductivity, and finds extensive use as an electrical conductor, thermal conductor, as a building material, and as a component of various alloys (http://en.wikipedia.org/wiki/Copper).

Clarke of Cu in soil amount to 30 mg/kg (Bowen, 1979). Cu average in the topsoil amount 53 mg/kg in range 11 – 92 mg/kg and for the bottom soil 52 mg/kg in range 12 – 99 mg/kg (Tabs. 5 and 6). For Cu is important that there is not large difference in concentration between the Cu concentrations in both soil horizons (Fig. 20). Cu average in the attic dust (181 mg/kg) exceeds estimated average in the surrounding samples of topsoil 2.2 times, which explain its anthropogenic nature (Fig. 19).

The highest concentrations of Cu in both soil horizons are found closer to ironworks Zenica (Figs. 26 and 35). In the mentioned region (17 locations around ironworks) average Cu in topsoil 68 mg/kg and bottom soil 70 mg/kg, what exceed estimated concentration of surrounding (68 mg/kg – topsoil and 70 mg/kg – bottom soil) about 50 % (Fig. 26).

The main source of Cu pollution is consequence of ironworks activity, but also natural source is important. According to the Slovenian legislation (Ur. list RS 68/96 –Tab. 2) concentrations of Cu exceed the Limit value about 14km2 in both soil horizons (Fig. 36). Concentrations of Cu do not exceed the Warning values.

Figure 35: Spatial copper distribution in topsoil (above) and bottom soil (below)

Figure 36: Spatial copper pollution in topsoil (above) and bottom soil (below) according to the Slovenian legislation (Ur. List RS 68/96)

76 6.3.6. Mercury (Hg)

Mercury, also called quicksilver, has the symbol Hg, atomic number 80, and is found in the 12th group of the periodic table. A heavy, silver transition metal, mercury is one of elements that are liquid. Hg can be found either as a native or in minerals: cinnabar (HgS), corderoite, livingstonite and other. In nature Hg occur in three oxidation states: Hg(0), Hg (I), Hg (II). Quicksilver uses in chemical industry, electro industry, agriculture, paper industry, dental amalgams, colour production, etc. (Magos, 1987, 421)

Clarke of Hg in soil amount 60 µg/kg (Bowen, 1979). Hg average in the topsoil amount to 222 µg/kg in range 53 – 2973 µg/kg and for the bottom soil 157 µg/kg in range 58 – 959 µg/kg (Tabs. 5 and 6). For Hg, differences between concentrations of both topsoil and bottom soil are significant. Concentrations of the Hg in topsoil exceed concentrations in bottom soil about 40 % (Fig. 20). Hg average of attic dust (1804 µg/kg) exceed estimated average of the surroundings samples of topsoil (Fig. 19) more than 3.5 times, which explain its anthropogenic nature solely.

The highest concentrations of Hg in both soil horizons are found closer to ironworks Zenica (Figs. 26 and 37). In mentioned region (17 locations around ironworks) average of Hg in topsoil (424 µg/kg) and in bottom soil (339 µg/kg) exceed estimated average of the surrounding (167 µg/kg – topsoil i 115 µg/kg – bottom soil) more than 2.5 times (Fig 26).

The main source of Hg pollution is consequence of ironworks activity. Pollution of study area with Hg is no significant (Ur. list RS 68/96 – Tab. 2). Concentrations of Hg exceed the Limit value only in one sampling point. According to the law regulation, there is no pollution with Hg (Fig. 38).

Figure 37: Spatial mercury distribution in topsoil (above) and bottom soil (below)

Figure 38: Spatial mercury pollution in topsoil (above) and bottom soil (below) according to the Slovenian legislation (Ur. List RS 68/96)

79 6.3.7. Nickel (Ni)

Nickel is lustrous, metallic, silvery tinge, hard and ductile transitional metal in 10th group of periodic table with atomic number 28. It occurs combined with sulphur in millerite, with arsenic in the mineral niccolite, and with arsenic and sulphur in nickel glance. Because of its permanence in air and its inertness to oxidation, it is used in coins, for plating iron brass, etc., for chemical apparatus, and in certain alloys. Nickel is used in many industrial and consumer products, including stainless steel, magnets, coinage, and special alloys. It is also used for plating and as a green tint in glass. Nickel is pre-eminently an alloy metal (Cu, Cr, Al, Pb, Co, Ag and Au), and its chief use is in the nickel steels and nickel cast irons, of which there are innumerable varieties (http://en.wikipedia.org/wiki/Nickel).

Clarke of Ni in soil amount to 40 mg/kg (Rösler & Lange, 1972). Ni average in the topsoil for study area amount 122 mg/kg in range 47 – 329 mg/kg and for the bottom soil 131 mg/kg in range 51 – 338 mg/kg (Tabs. 5 and 6). Concentrations of Ni in bottom soil exceed the concentrations in topsoil about 30 % (Fig. 20). Ni average in attic dust (156 mg/kg) exceeds estimated average Ni in the surrounding samples of topsoil about 30 % (Fig. 19). Also for Ni distribution, it is possible to say that its distribution is natural.

Similarly to the Co and Cr, the lowest concentrations of Ni (108 mg/kg – topsoil and 111 mg/kg -bottom soil) have found on outcrop areas of the Miocene clastites and the Quaternary Alluvium, and the highest concentrations of Ni on the Jurassic-Cretaceous flysch rocks – the Vranduk series (183 mg/kg – topsoil and 190 mg/kg – bottom soil) (Figs. 24 and 39). Concentrations of Ni increase with depth, especially in the Vranduk series, what explain its natural distribution. The maximum values of Ni have found on left side of the valley in settlement Kozarci, but high values have found in settlements D. Gračanica and Sviće. High concentrations are consequence of geological background and are slightly changed with the depth.

According to the law regulation (Ur. list RS 68/96 –Tab. 2) natural pollution with Ni is significant. Values of Ni exceed the limit and warning value in almost all study area (about 51 km2 in both soil horizons) and the critical value in topsoil about 2 km2 and 2.7 km2 in bottom soil (Fig. 40).

Figure 39: Spatial nickel distribution in topsoil (above) and bottom soil (below)

Figure 40: Spatial nickel pollution in topsoil (above) and bottom soil (below) according to the Slovenian legislation (Ur. List RS 68/96)

82 6.3.8. Lead (Pb)

Lead is a transition metal in 14th group of periodic table with atomic number 82. The main ores of Pb are galena (PbS) and cerusite (PbCO3), but also in ores anglesite (PbSO4) and crocoite (PbCrO4) (Filipović & Lipanović, 1995). Anthropogenic emission of Pb is much higher than natural whereas biggest part is from internal combustion engine, burning of ore that contain Pb, uses of different Pb material removing of waste materials, making of colours, uses of some insecticide and burning of fossil fuels (Greenwood, 1984). Use of Pb as a fuel additive, its concentration in last 80 to 100 years has increased in environment (Hill, 1992).

Clarke of Pb in soil amount to 35 mg/kg (Bowen, 1979). Pb average in the topsoil amount 122 mg/kg in range 19 – 384 mg/kg and for the bottom soil 87 mg/kg in range 14 – 488 mg/kg (Tabs. 5 and 6). For Pb, differences between concentrations of both, topsoil and bottom soil are significant. Concentrations of Pb in topsoil exceed the concentrations in bottom soil about 40 % (Fig. 20). Pb value in the attic dust (982 mg/kg) exceeds estimated average in surrounding samples of topsoil 3.7 times (Fig. 19), which explain its anthropogenic distribution.

High concentrations of Pb in both soil horizons are found closer to ironworks Zenica in settlements N. Tetovo and Podnožje, and maximum concentration on SE of the industrial zone, on the alluvium between the river and ironworks (Figs. 26 and 41). In the mentioned region (17 locations around ironworks) average Pb amount in topsoil (207 mg/kg) and in bottom soil (188 mg/kg), exceed estimated average of surrounding (97 mg/kg – topsoil and 65 mg/kg – bottom soil) more than 2.5 times (Fig. 26).

The main source of Pb pollution is consequence of ironworks activity, but influence of traffic in the Zenica valley is important. Pollution of study area with Pb is significant. Concentrations of Pb exceed the limit value in 43 km2 in topsoil and in 26 km2 in bottom soil. Warning value for Pb is exceeded on 30 km2 in both soil horizons on 16 km2. Concentrations of Pb do not exceed the critical value (Fig. 42).

Figure 41: Spatial lead distribution in topsoil (above) and bottom soil (below)

Figure 42: Spatial lead pollution in topsoil (above) and bottom soil (below) according to the Slovenian legislation (Ur. List RS 68/96)

85 6.3.9. Zinc (Zn)

Zink is transition metal in 12th group of periodic table with atomic number 30. In nature occur in oxidation state (II). The main ore of Zn in sphalerite (ZnS), very often is associated with other chemical elements molecules (such as chlorides, oxides, sulphides and sulphates). Most important anthropogenic sources of Zn are metallurgy industry, burning of fossil fuels, mines and Zn ore processing. Most of Zn is used in car industries, alloys, and galvanisation procedures, industry of colours, lacquers and ointments. Zn is often present also in urban regions where originates above all from industry activities, traffic (Adriano, 1986). Zn is for living organism (plants, animals and humans) essential chemical element that has important role in enzymes processes. Toxicity of Zn is relatively low, however there are cases when poisoning with Zn occur, that are most often showed as anaemia, injuries of pancreas and damage kidneys and liver.

Clarke of Zn in soil amount to 90 mg/kg (Bowen, 1979). Zn average in the topsoil amount 202 mg/kg in range 46 – 474 mg/kg and for the bottom soil 167 mg/kg in range 36 – 555 mg/kg (Tabs. 5 and 6). As well as Cd, Cu Hg and Pb, also for Zn difference between topsoil and bottom soil is significant (Figs. 20). Concentrations of Zn in topsoil exceed the concentration in bottom soil about 20 %. Zn average in attic dust (1204 mg/kg) rapidly exceeds estimated average of the surroundings samples of topsoil for 2.7 times (Fig. 19), which explain its anthropogenic distribution.

The highest concentrations of Zn in both soil horizons are found close to the ironworks, on its southern and SE part (Figs. 26 and 43). Regard to geological background, the maximum values have found on alluvium. In mentioned region (17 locations around ironworks) average Zn amount in topsoil 306 mg/kg and in bottom soil 285 mg/kg, and exceed estimated average of town surrounding (168 mg/kg – topsoil and 135 mg/kg – bottom soil) more than 2.5 times (Fig. 26).

The main source of Zn pollution is consequence of ironworks activity, pollution of the study area with Zn is significant. (Ur. list RS 68/96 – Tab. 2). Concentrations of Zn exceed the limit value in 21 km2 in topsoil and in 13 km2 in bottom soil. Warning value for Zn is exceeded on 7 km2 in topsoil and in bottom soil on 5 km2. Concentrations of Zn do not exceed the critical value (Fig. 44).

Figure 43: Spatial zinc distribution in topsoil (above) and bottom soil (below)

Figure 44: Spatial zinc pollution in topsoil (above) and bottom soil (below) according to the Slovenian legislation (Ur. List RS 68/96)

88 6.4. SOIL POLLUTION OF ZENICA AREA

Due to research work have been considered that concentration of any mentioned 10 chemical elements (As, Cd, Co, Cr, Cu, Hg, Ni, Mo, Pb and Zn), that are set out in the Slovenian laws and legislations (Ur. List RS, 68/96) exceed warning value in almost all study area (51 km2) in both soil horizons. Critical values have found on 3.9 km2 in topsoil and 5.4 km2 in bottom soil. However, total pollution is not only a consequence of anthropogenic activities, especially historical period of Zenica ironworking.

Within the data processing (chapters 6.1. and 6.3.) high concentrations of Co, Cr and Ni as a result of natural processes were determined - weathering processes of rock rich with above mentioned elements (primary ophiolites have been formed Jurassic, Cretaceous, Paleogene flysch and Neogene clastic series). This is quite common process not only in Bosnia and Herzegovina. Similar relations have been considered in soils formed on same outcrop formations in Slovenia and Croatia (Šajn et al., 2005). Examining of total naturally pollution of soil (Fig. 45) that associate high concentrations Co, Cr and Ni have found almost in all study area (51 km2) where concentrations of mentioned elements exceed the warning value. Critical value of mentioned elements is found on 2 km2 in topsoil and 3.3 km2 in bottom soil. Natural critically polluted area is located on surrounding hills, outside from main urban zone and we cannot talk about another anthropogenic source of those elements. The main share in total natural pollution is principally Ni (Fig. 40) and Cr (Fig. 34).

Anthropogenic pollution which is consequence of historical activities of the ironworks Zenica, but also coal mining and other anthropogenic influence (such as traffic and household activities) that associate high concentrations of As, Cd, Cu, Hg, Pb and Zn (chapters 6.2. and 6.3.). The high concentrations of the mention elements exceed the limit value on 48 km2 in both soil horizons, what is majority of the study area. Warning value is exceeded on 37 km2 in topsoil and 34 km2 in bottom soil, and the critical value on 2 km2 in both soil horizons (Fig. 46). For the mentioned group of elements is significant that polluted area occupy the Zenica basin and area among the river Bosna. Relatively high concentrations of group on surroundings hills are consequence of climate conditions – locale winds (Fig 46). Critically polluted area is mainly situated on the Miocene coal layers on the NW side of study area (N. Tetovo) and refers to As distribution (Fig. 28). In this case, consequences of mining, and less of long period of ironworks working are claimed.

Figure 45: Spatial natural origin pollution in topsoil (above) and bottom soil (below) according to the Slovenian legislation (Ur. List RS 68/96)

Figure 46: Spatial anthropogenical pollution in topsoil (above) and bottom soil (below) according to the Slovenian legislation (Ur. List RS 68/96)

91 Table 9: Slovenian averages in topsoil (Šajn, 2003) and average values of seven selected chemical elements (Alijagić & Šajn, 2006) for considered ironworks in Slovenia and B&H. (Concentrations of Hg are expressed in µg/kg, remaining elements in mg/kg)

Topsoil (0-5 cm) Attic dust Slo Je Št Ra Ze Va Je Št Ra Ze Va

As 14 19 28 20 57 31 44 116 28 121 83 Cd 0.45 1.9 4.9 2.1 1.5 3.5 5.8 37 6.2 4.3 9.0 Cu 31 80 638 137 84 183 161 430 323 181 400 Hg 650 586 628 218 515 1135 2633 1813 285 1804 3636 Mo 0.80 7.0 2.5 33 1.8 5.2 22 26 214 5.3 16 Pb 42 430 175 500 267 918 1651 1368 1223 982 2412 Zn 124 828 706 1431 441 2434 2200 6835 1911 1204 5830

Slo – Slovenian average; Je – Jesenice, Št – Štore; Ra – Ravne; Ze – Zenica; Va - Vareš

(Slovenian topsoil (Slovenian topsoil 10 /C

5 Attic dust Enrichment ratio Enrichment 0 a e

(group of samples) of (group Topsoil o) Ar

C l ) S lo ( S o) e ( l ) ic e (S H ) n r i H se to ne (B i e S v B J a ca ( R ni es e ar Z V Elements

Figure 47: Average enrichment ratios (group of samples/Slovenian topsoil) of As,Cd, Cu, Hg, Mo, Pb and Zn with regard location of sampling (data: Alijagić & Šajn, 2006)

92 Comparation As, Cd, Cu, Hg, Mo, Pb and Zn concentrations in pilot samples of topsoil and attic dust (Alijagić & Šajn, 2006), collected close to ironworks in Slovenia (Jesenice, Štore, Ravne) and also in Bosnia and Herzegovina (Zenica, Vareš) (Tab. 9 and Fig. 47) have found relatively low pollution with heavy metals in Zenica basin, regardless that this ironwork has been the biggest one in former Yugoslavia. In comparison with average of mentioned elements in Slovenian topsoil (Šajn, 2003) in area around ironworks Zenica enrichment ratio (ER) in topsoil amount c. 4 times and in attic dust c. 11 times as well, what is considerably lower from ER on area close to ironworks Štore in Slovenia (c. 6 times - topsoil and c. 29 times - attic dust) or around ironworks Vareš in Bosnia and Herzegovina (c. 9 times - topsoil and c. 24 times - attic dust).

Similarly is considered that anthropogenically critical polluted soils c. 2 km2 near to ironworks Zenica is unimportant compare to critical polluted area around ironworks Jesenice in Slovenia (13 km2), which has been second largest ironworks in former Yugoslavia (Šajn & Gosar, 2004).

93 7. CONCLUSION

The Master thesis is made within researches that are achieved in territory of Bosnia and Herzegovina under bilateral project between Geological survey of Slovenia and Faculty of Natural Sciences, at University of Sarajevo (BI-BA/04-05-009) in period 2004 - 2006.

The objectives of this work have been: distribution of the chemical elements in attic dust, topsoil and bottom soil; statistical determination of main geochemical groups and their spatial distribution in soil; identification, of geogenic (natural) geochemical background and anthropogenic (man-made) element sources and determination of the spatial pollution with heavy metals in topsoil and bottom soil.

At 62 different sites, 124 samples of attic dust, topsoil (0-5 cm depth) and bottom soil (20-30 cm depth), on 52 km2 of the Zenica area were collected. Analysis for 42 chemical elements (Al, Ca, Fe, K, Mg, Na, P, S, Ti, Ag, As, Au, Ba, Be, Bi, Cd, Ce Co, Cr, Cu, Hg, Hf, La, Li, Mn, Mo, Nb, Ni, Pb, Rb, Sb, Sc, Sn, Sr, Ta, Th, U, V, W, Y, Zn and Zr) was performed.

Two geogenic and one anthropogenic geochemical association were established on the basis of: visually indicated similarity of geographic distribution of elemental patterns in the topsoil and bottom soil; comparisons of basic statistics, correlation coefficient matrices; results of cluster and factor analyses and comparisons of enrichment ratios.

Two natural geochemical associations (Al, Ca, Ce, K, La, Li, Nb, Rb, Sc, Ta, Ti Th, V and Y) and (Co, Cr, Na, Ni and Mg) are influenced mainly by lithology, but the third anthropogenic association (Ag, Bi, Cd, Cu, Hg, Mo, Pb, Sb and Zn) is result of historical activities of the ironworks Zenica, but also coal mining and other anthropogenic influences iron metallurgy in the past.

High concentrations of Co, Cr and Ni are result of weathering processes of rock rich with the mentioned elements. Total naturally pollution of soil have found almost in all study area where concentrations exceed the warning level. Critical level of the mentioned elements is found on c. 2 km2 in topsoil and c. 3.3 km2 in bottom soil. Natural critically polluted area is

94 located on surrounding hills, outside from main the urban zone. The main share in total natural pollution is principally Ni and Cr.

Anthropogenic pollution that associate high concentrations of As, Cd, Cu, Hg, Pb and Zn, exceed warning level on 37 km2 in topsoil and 34 km2 in bottom soil but critical level on c. 2 km2 in both soil horizons. For the mentioned association is significant that polluted area is situated in the Zenica basin and area among the river Bosna. Critically polluted area is mainly situated on the Miocene coal layers on the NW side of study area and refers to As distribution.

Comparation concentrations of As, Cd, Cu, Hg, Mo, Pb and Zn in pilot samples of topsoil and attic dust, collected close to ironworks in Slovenia and also in Bosnia and Herzegovina have found relatively low pollution with heavy metals in Zenica basin, regardless that this ironwork has been the biggest one in former Yugoslavia. Similarly is considered that anthropogenically critical polluted soils c. 2 km2 near to ironworks Zenica is unimportant compare to critical polluted area around ironworks Jesenice (13 km2), which has been second largest ironworks in former Yugoslavia.

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8.1. HTTP SOURCES http://en.wikipedia.org/wiki/Copper (Copper - Wikipedia, the free encyclopedia) http://en.wikipedia.org/wiki/Nickel (Nickel - Wikipedia, the free encyclopedia) http://georem.mpch-mainz.gwdg.de/sample_query.asp (GeoReM - Geological and environmental reference materials) http://jan.ucc.nau.edu/ doetqp/courses/ env320/lec3/ Lec3.html (Soil Formation - Chapter 2) http://web.missouri.edu/~umcreactorweb/pages/ac_icpms1.shtml (Inductively Coupled Pla- sma Mass Spectrometry - ICP-MS) http://www.bhsteel.com.ba/istorija.htm (Official website of Ironworks Zenica) http://www.contaminatedland.co.uk/std-guid/dutch-l.htm (The new Dutchlist)

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100