Environmental Earth Sciences

, Volume 72, Issue 10, pp 3939–3953 | Cite as

Magnetic, geochemical and mineralogical properties of sediments from karstic and flysch rivers of Croatia and Slovenia

  • Stanislav Frančišković-Bilinski
  • Robert Scholger
  • Halka Bilinski
  • Darko Tibljaš
Original Article


The aim of the present work was to investigate links between the low-field magnetic susceptibility (MS) and chemical and mineral composition of sediments from several Croatian and Slovenian rivers, as well as to determine possible anthropogenic influence on these sediments. MS measurements are a fast and simple method, which serves as a proxy for the estimation of pollution in different environmental systems. The investigated rivers are predominantly unpolluted rivers from Croatian and Slovenian karstic and flysch areas, which belong to the Adriatic or the Black Sea watersheds: the Dragonja, the Mirna, the Raša, the Rižana, the Reka, the Rak, the Cerknišnica, the Unec and the Ljubljanica rivers. It was assumed that, due to their mostly unpolluted status, they could serve as a database for natural MS background values for this region. For comparison, several rivers and a lake from the Celje old metallurgic industrial area (Slovenia) were also investigated: the Savinja, the Hudinja, the Voglajna rivers and Slivniško Lake. They form a sub-basin of the Sava River drainage basin. Sediments of the clean karstic and flysch rivers showed extremely low MS values, with mass susceptibility values ranging from 0.58 × 10−7 to 5.11 × 10−7 m3/kg, and isothermal remanent magnetism (IRM) values ranging from 0.71 to 7.88 A/m. In the Celje industrial area, river sediments showed much higher MS values, with mass susceptibility values ranging from 1.31 × 10−7 to 38.3 × 10−7 m3/kg, and IRM values ranging from 0.91 to 100.42 A/m. The highest MS value was found in the Voglajna River at Teharje-Štore, a point which showed a significant number of anomalies of toxic metals in earlier investigations. Semiquantitative determination of relations between grain size and concentration of magnetite was performed using the Thompson-Oldfield method. X-ray diffraction (XRD) mineralogical analysis showed that sediments of the Celje area have mostly quartz as major mineral, with relatively small amount of carbonate minerals, while in sediments of karstic rivers carbonate minerals prevail. Statistically significant correlations were obtained between MS and Cr, Mn, Fe, Co, Ni, Cu, Zn, Cd and Ba in the Slovenian karstic region and between MS and Cr, Fe, Co, Ni and Zn in flysch drainage basins. On the contrary, no correlation of MS and Hg content was obtained.


Karstic and flysch rivers Croatia Slovenia Magnetic susceptibility Trace elements Heavy metals Sediments Mineralogy Anthropogenic influence 



Field work was organized within the Croatian–Slovenian bilateral project (2001–2003), principal investigators H. Bilinski and D. Hanžel. Magnetic measurements were performed at the Montanuniversität Leoben and at its Paleomagnetic Laboratory in Gams. A short stay of S. F–B. in Austria was covered from the Croatian–Austrian bilateral project (2010-2011), principal investigators S. Frančišković-Bilinski and T. Hofmann. Additional expenses were covered from projects of Croatian Ministry of Science Education and Sport No. 098-0982934-2720 (Principal investigator I. Pižeta) and No. 119-1191155-1156 (Principal investigator D. Balen). Authors are grateful to R. Košćal for preparing graphics. We also thank three anonymous reviewers, whose suggestions helped a lot to improve the overall quality of manuscript.


  1. Babić LJ, Ćorić S, Hernitz-Kučenjak M, Zupanič J (2007) The Middle Eocene age of the supposed late Oligocene sediments in the flysch of the Pazin Basin (Istria, outer Dinarides). Nat Croatica Periodicum Musei historiae naturalis Croatici 16(2):83–103Google Scholar
  2. Barišić D, Marović G, Senčar J, Lulić S (2001) Natural radionuclides in slag/ash pile from coal-fired power plant Plomin. In: Obelić, Bogomil; Ranogajec-Komor, Maria; Miljanić, Saveta; Krajcar Bronić, Ines (eds) Proceedings of the IRPA Regional Congress on Radiation Protection in Central Europe “Radiation Protection and Health”—Zagreb: HDZZ/CRPAGoogle Scholar
  3. Botsou F, Karageorgis AP, Dassenakis E, Scoullos M (2011) Assessment of heavy metal contamination and mineral magnetic characterization of the Asopos River sediments (Central Greece). Mar Pollut Bull 62(3):547–563CrossRefGoogle Scholar
  4. Boyko T, Scholger R, Stanjek H (2004) Topsoil magnetic susceptibility mapping as a tool for pollution monitoring: repeatability of in situ measurements. J Appl Geophys 55(3–4):249–259CrossRefGoogle Scholar
  5. Chen M, Ma QL (2001) Comparison of three aqua regia digestion methods for twenty Florida soils. Soil Sci Soc Am J 65:491–499CrossRefGoogle Scholar
  6. Dlouha Š, Petrovsky E, Kapička A, Borüvka L, Ash C, Drábek O (2013) Investigation of polluted alluvial soils by magnetic susceptibility methods: a case study of the Litavka River. Soil Water Res 8(4):151–157Google Scholar
  7. FGI (1970) Geological map of SFR Yugoslavia 1:500 000. Federal Geological Institute, BeogradGoogle Scholar
  8. Fialová H, Maier G, Petrovsky E, Kapička A, Boyko T, Scholger R (2006) MAGPROX Team. Magnetic properties of soils from sites with different geological and environmental settings. Appl Geophys 59:273–283CrossRefGoogle Scholar
  9. Frančišković-Bilinski S (2008a) Detection of coal combustion products in stream sediments by chemical analysis and magnetic susceptibility measurements. Mineral Mag 72:43–48CrossRefGoogle Scholar
  10. Frančišković-Bilinski S (2008b) Detection of geochemical anomalies in stream sediments of the upper Sava River drainage basin (Slovenia, Croatia). Fresenius Environ Bull 17(2):188–196Google Scholar
  11. Frančišković-Bilinski S, Bilinski H, Tibljaš D, Hanžel D (2003) Characterization of sediments from Dragonja, river at the border line between Croatia and Slovenia (In Croatian-with an English summary). In: 3rd Croatian Conference on Waters, Osijek, Croatia, pp 1147–1154Google Scholar
  12. Frančišković-Bilinski S, Bilinski H, Darko Tibljaš, Rantitsch G (2005) Effects of mercury mining regions from NW Dinarides on quality of stream sediments. Fresenius Environ Bull 14(10):913–927Google Scholar
  13. Frančišković-Bilinski S, Bilinski H, Tibljaš D, Hanžel D (2006) Sediments from Savinja, Voglajna and Hudinja rivers (Slovenia), reflecting anomalies in an old metallurgic area. Fresenius Environ Bull 15(3):220–228Google Scholar
  14. Frančišković-Bilinski S, Bilinski H, Tibljaš D (2007) Contamination status of flysch-draining rivers of Croatia and Slovenia, flowing to the north Adriatic Sea. In: Briand F, Sakellariou D, Font J, Fisher N (eds) Abstracts of the 38th CIESM congress, Commission internationale pour l’exploration scientifique de la mer Méditerranée. CIESM, Monaco, pp 90–90Google Scholar
  15. Frančišković-Bilinski S, Bilinski H, Scholger R, Tomašić N, Maldini K (2014) Magnetic spherules in sediments of the karstic Dobra River (Croatia). J Soils Sediments. doi: 10.1007/s11368-013-0808-x Google Scholar
  16. Gams I (2004) Kras v Sloveniji. Založba ZRC pp 515Google Scholar
  17. Halamić J, Miko S (2009) Geochemical atlas of the Republic of Croatia. Croatian Geological Survey, Zagreb, p 87Google Scholar
  18. Hanesch M, Scholger R (2002) Monitoring of heavy metal loadings in soils by means of magnetic susceptibility measurements. Environ Geol 42:857–870CrossRefGoogle Scholar
  19. Hanesch M, Scholger R, Rey D (2003) Mapping dust distribution around an industrial site by measuring magnetic parameters of tree leaves. Atmos Environ 37:5125–5133CrossRefGoogle Scholar
  20. Hay KL, Dearing JA, Baban SMJ, Loveland P (1997) A preliminary attempt to identify atmospherically derived pollution particles in English topsoils from magnetic susceptibility measurements. Phys Chem Earth 22(1–2):207–210CrossRefGoogle Scholar
  21. Heller F, Strzyszcz Z, Magiera T (1998) Magnetic record of industrial pollution in forest soils of Upper Silesia, Poland. J Geophys Res 103(B8):17767–17774CrossRefGoogle Scholar
  22. Kapička A, Petrovský E, Ustjak S, Macháčková K (1999) Proxy mapping of fly ash pollution of soils around a coal-burning power plant. J Geochem Explor 66:291–297CrossRefGoogle Scholar
  23. Kogovšek J (2001) Observations of the Reka flood pulse in May 1999. Acta Carsologica 30/1, 4:55–68Google Scholar
  24. Magdalenić Z (1972) Sedimentology of central Istria flysch deposits (in Croatian with English summary). Acta Geologica 7/2:1–34, 71–101Google Scholar
  25. Mikes T, Dunkl I, Frisch W, von Eynatten H (2006) Geochemistry of Eocene flysch sandstones in the NW External Dinarides. Acta Geol Hung 49(2):103–124CrossRefGoogle Scholar
  26. Novakova T, Grygar TM, Babek O, Famera M, Mihaljević M, Strnad L (2012) Distinguishing regional and local sources of pollution by trace metals and magnetic particles in fluvial sediments of the Morava River, Czech Republic. J Soils Sediments. 14 December 2012, p 14. doi: 10.1007/s11368-012-0632-8
  27. Oldfield F, Hunt A, Jones MDH, Chester R, Dearing JA, Olsson L, Prospero JM (1985) Magnetic differentiation of atmospheric dusts. Nature 317:516–518CrossRefGoogle Scholar
  28. Petrovský E, Ellwood BB (1999) Magnetic monitoring of air-, land-, and water-pollution. In: Maher BA, Thompson R (eds) Quaternary Climates, Environments and Magnetism. Cambridge University Press, Cambridge, pp 279–322CrossRefGoogle Scholar
  29. Petrovsky E, Kapička A, Jordanova N, Knab M, Hoffmann V (2000) Low-field magnetic susceptibility: a proxy method of estimating increased pollution of different environmental systems. Environ Geol 39(3–4):312–318Google Scholar
  30. Philips Analytical B.V. (2001) High Score ver. 1.0. AlmeloGoogle Scholar
  31. Plater AJ, Ridgeway J, Appleby PG, Berry A, Wright MR (1998) Historical contaminant fluxes in the Tees estuary, UK. Mar Pollut Bull 37:343–360CrossRefGoogle Scholar
  32. Poje M (2008) Kakovost površinskih virov pitne vode v Sloveniji. Agencija Republike Slovenije za okolje, Ljubljana, pp 39. http://www.arso.gov.si/vode/reke/publikacije%20in%20poro%C4%8Dila/PVOPV_publikacija-01.pdf
  33. Powder Diffraction File (1997) International Centre for Diffraction Data, Newtown Square, Pennsylvania, USAGoogle Scholar
  34. Reimann C, Filzmoser P, Garrett RG (2005) Background and threshold: critical comparison of methods of determination. Sci Total Environ 346:1–16CrossRefGoogle Scholar
  35. Salminen R, Tarvainen T (1997) The problem of defining geochemical baselines. A case study of selected elements and geological materials in Finland. J Geochem Explor 60:91–98CrossRefGoogle Scholar
  36. Scholger R (1998) Heavy metal pollution monitoring by magnetic susceptibility measurements applied to sediments of the river Mur (Styria, Austria). Eur J Environ Eng Geophys 3:25–37Google Scholar
  37. Shoumkova A (2006) Physico-chemical characterization and magnetic separation of coal fly ashes from “Varna”, “Bobov Dol” and “Maritza-Istok I” power plants, Bulgaria. II—magnetic separation. J Univ Chem Technol Metall 41(2):181–186Google Scholar
  38. SMSP and Falconbridge NC SAS (2005) Koniambo project, Environmental and social impact assessment, Chapter 4 Mine, 4.2-7 Quality criteria for freshwater sediment. Available at: http://www.koniambo-nickel.com/en/pdf/02_Appendices/ESIA_Volume%20II_TOC_Rev_1_2.pdf
  39. Šoltes I (2010) Sanacija starih bremen industrijskih odpadkov in nedovoljenih odlagališč gradbenih odpadkov. The Court of Audit of Republic of Slovenia. p 61. http://www.rs-rs.si/rsrs/rsrs.nsf/I/KABD7677C5FCE2EFFC125774B0029896C/$file/MOPIndOdpad.SP04-08.pdf
  40. Sondi I, Juračić M, Prohić E, Pravdić V (1994) Particulate sand the environmental capacity for trace metals—a small river as a model for a land-sea transfer system—the Raša River estuary. Sci Total Environ 155(2):173–185CrossRefGoogle Scholar
  41. Sondi I, Juračić M, Pravdić V (1995) Sedimentation in a disequilibrium river-dominated estuary—the Raša River estuary (Adriatic Sea, Croatia). Sedimentology 42(5):769–782CrossRefGoogle Scholar
  42. StatSoft Inc. (2007) STATISTICA (data analysis software system), version 8. www.statsoft.com
  43. Štern J, Förstner U (1976) Heavy metals distribution in the sediment of the Sava Basin in Slovenia. Geologija 19:259–274Google Scholar
  44. Strzyszcz Z (1993) Magnetic susceptibility of soils in the areas influenced by industrial emissions. In: Schulin R (ed) soil monitoring, Monte Verita, Birkhäuser Verlag, Basel, pp 255–269Google Scholar
  45. Strzyszcz Z, Magiera T, Heller F (1996) The influence of industrial emissions on the magnetic susceptibility of soils in Upper Silesia. Studia geophisica et geodetica 40:276–286CrossRefGoogle Scholar
  46. Thompson R, Oldfield F (1986) Environmental magnetism. Allen & Unwin, LondonCrossRefGoogle Scholar
  47. Tukey JW (1977) Exploratory data analysis. Addison-Wesley, Menlo Park ISBN0-201-07616-0Google Scholar
  48. Zhang C, Qiao Q, Piper JDA, Huang B (2011) Assessment of heavy metal pollution from a Fe-smelting plant in urban river sediments using environmental magnetic and geochemical methods. Environ Pollut 159:3057–3070CrossRefGoogle Scholar

Copyright information

© Springer-Verlag Berlin Heidelberg 2014

Authors and Affiliations

  • Stanislav Frančišković-Bilinski
    • 1
  • Robert Scholger
    • 2
  • Halka Bilinski
    • 1
  • Darko Tibljaš
    • 3
  1. 1.Division for Marine and Environmental ResearchInstitute Ruđer BoškovićZagrebCroatia
  2. 2.Department of Applied Geosciences and GeophysicsMontanuniversität LeobenLeobenAustria
  3. 3.Institute of Mineralogy and Petrology, Department of Geology, Faculty of ScienceUniversity of ZagrebZagrebCroatia

Personalised recommendations