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 1 © 2007 Jasminka Alijagić All rights reserved 2 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 4 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 6 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