Environmental geochemistry of the polymetallic ore deposits: Case studies from the Rude and the Sv. Jakob historical mining sites, NW Croatia
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Published:
Jun 6, 2013
Keywords:
polymetallic ore deposits, heavy metal pollution, stream water and sediments, Samoborska Gora Mts., Medvednica Mts., NW Croatia
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Abstract
This paper presents the results of the sampling surveys carried out in order to evaluate the environmental impact of the Rude and the Sv. Jakob historical mining sites, NW Croatia. The studied polymetallic ore deposits are differing in the mineralogical and geochemical features as well as in the host rock lithology. The Rude Fe-Cu-Pb-Zn-Ba deposit is hosted by Permian siliciclastic sediments. Siderite, hematite, galena, sphalerite, chalcopyrite, pyrite, barite and gypsum are the major ore minerals, whereas quartz is the principal gangue mineral. The Sv. Jakob Pb-Zn-Ag deposit occurs in the Middle Triassic dolostone. The most abundant ore minerals are galena, sphalerite and pyrite. Calcite and quartz represent the principal gangue minerals. Although the deposits represent the potential sources of numerous toxic metals, the pollution of the drainage streams and associated stream sediments was not recorded. The studied mining sites are characterized by the high carbonate/sulfide ratios responsible for the alkaline character of the drainage streams. Consequently, the mining sites have very low potential for generation of acid mine drainage as well as very low potential for leaching of heavy metals into the drainage systems. Furthermore, the presented study revealed that the populated areas (stream waters with decreased redox potential, increased organic matter content, high NO3-, NH4+ and PO43- concentrations; stream sediments enriched in exchangeable Pb and Zn) and the Sava river alluvium (overflowing streams enriched in Hg) represent bigger environmental threat than the investigated polymetallic ore deposits.
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References
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ÐURÐANOVIĆ, Ž. (1973): O paleozoiku i trijasu Medvednice (Zagrebaèke gore) i područja Dvora na Uni na temelju konodonta [About the Paleozoic and the Triassic of Medvednica Mt. and the area near Dvor na Uni on the basis of conodonts– in Croatian]. -Geol. Vjesn., Zagreb, 25, 29-49.
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FENG, X.H., ZHAI, L.M., TAN, W.F., LIU, F. & HE, J.Z. (2007): Adsorption and redox reactions of heavy metals on synthesized Mn oxide minerals. –Environ. Pollut.,147, 366-373.
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GUNDERSEN, P. & STEINNES, E. (2003): Influence of pH and TOC concentration on Cu, Zn, Cd, and Al speciation in rivers. -Water Res., 37, 307–318.
GUNGOR, E.B.O. & BEKBOLET, M. (2010): Zinc release by humic and fulvic acid as influenced by pH, complexation and DOC sorption. –Geoderma, 159,131–138.
HALAMIĆ, J., PEH, Z., BUKOVEC, D., MIKO, S. & GALOVIĆ, L. (2001): A factor model of the relationship between stream sediment geochemistry and adjacent drainage basin lithology, Medvednica Mt., Croatia. –Geol. Croat., 54, 37-51.
HALAMIĆ, J., GALOVIĆ, L. & ŠPARICA, M. (2003): Heavy metal (As, Cd, Cu, Hg, Pb and Zn) distribution in topsoil developed on alluvial sediments of the Drava and Sava rivers in NW Croatia. –Geol. Croat., 56, 215-232.
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HERAK, M. (1956): Geologija Samoborskog gorja. –Acta geol., JAZU, Zagreb, I, 49–74.
HUANG, X., SILLANPÄÄ, M., GJESSING, E.T., PERÄNIEMI, S. & VOGT, R.D. (2010): Environmental impact of mining activities on the surface water quality in Tibet: Gyama valley. -Sci Total Environ., 408, 4177-4184.
JAMES, R.O. & MACNAUGHTON, M.G. (1977): The adsorption of aqueous heavy metals on inorganic minerals. –Geochim. Cosmochim. Acta, 41, 1549-1555.
MASCARO, I., BENVENUTI, M., CORSINI, F., COSTAGLIOLA, P., LATTANZI, P. PARRINI, P. & TANELLI, G. (2001): Mine wastes at the polymetallic deposit of Fenice Capanne (Southern Tuscany, Italy): Mineralogy, geochemistry and environmental impact. –Environ. Geol., 41, 417–429.
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ÖZKARAOVA GUNGOR, E.B. & BEKBOLET, M. (2010) Zinc release by humic and fulvic acid as influenced by pH, complexation and DOC sorption. –Geoderma, 159,131–138.
PALINKAŠ, L., NAMJESNIK-DEJANOVIĆ, K., MIKO, S., DURN, G. & PIRC, S. (1996): Distribution of mercury, lead and cadmium in Zagreb city soils. –In: Richardson, M. (Ed.) Environmental xenobiotics, Taylor & Francis, London, 355-374.
PALINKAŠ, L., BOROJEVIĆ ŠOŠTARIĆ, S. & STRMIĆ PALINKAŠ, S. (2008): Metallogeny of the Northwestern and Central Dinarides and Southern Tisia. -Ore Geol. Rev., 34, 501-520.
PALINKAŠ, L., BOROJEVIĆ ŠOŠTARIĆ, S., STRMIĆ PALINKAŠ, S., PROCHASKA, W., SPANGENBERG, J., CUNA, S. & ŠINKOVEC, B. (2010): Permian–polysulphide-siderite–barite–haematite deposit Rude in Samoborska Gora Mts., Zagorje–Mid–Transdanubian zone of the Internal Dinarides. –Geol. Croat., 63, 93–115.
PAMIĆ, J. & TOMLJENOVIĆ, B. (1998): Basic geological data from the Croatian part of the Zagorje–Mid–Transdanubian Zone. –Acta Geol. Hungarica, 41, 389–400.
PEH, Z. (1992): Factor model of the geomorphological system of a part of Northwestern Croatia.- Geol. Croat., 45, 163-172.
PENG, J.-F., SONG, Y.-H., YUAN, P., CUI, X.-Y. & QIU, G.-L. (2009): The remediation of heavy metals contaminated sediment. -J. Hazard. Mater., 161, 633–640.
ROSE, A.W., DAHLBERG, E.C. & KEITH, M.L. (1970): A multiple regression technique for adjusting background values in stream sediment geochemistry. -Econ. Geol., 65, 156-165.
RYBICKA, E.H., CALMANO, W. & BREEGER, A. (1985): Heavy metals sorption/desorption on competing clay minerals; an experimental study. –Appl. Clay Sci., 9, 369-381.
ŠIKIĆ, K. (1995): Geološki vodič Medvednice.– Zagreb: Inst. geol.istraž., Zagreb, 199 p.
ŠIKIĆ, K., BASCH, O. & ŠIMUNIĆ, A. (1978): Osnovna geološka karta SFRJ 1:100 000. List Zagreb, L33–80 [Basic geological map of SFRY 1:100000, Zagreb sheet – in Croatian].– Inst. geol. istraž., Zagreb (1972), Sav. geol. zavod, Beograd.
ŠIKIĆ, K., BASCH, O. & ŠIMUNIĆ, A. (1979): Tumač osnovne geološke karte 1:100000, list Zagreb. –Sav. geol. zavod, Beograd, 81 p.
ŠINKOVEC, B. (1971): Geologija ležišta željezne i bakrene rude u Rudama kraj Samobora [Geology of iron and copper ore from Rude near Samobor – in Croatian]. –Geol. Vjesn., Zagreb, 24, 165–181.
ŠINKOVEC, B., PALINKAŠ, L. & DURN, G. (1988): Ore occurrences on Mt. Medvednica (in Croatian with English summary). -Geol. Vjesn., Zagreb, 41, 395–405.
SKOUSEN, J., RENTON, J., BROWN, H., EVANS, P., LEAVITT, B., BRADY, K., COHEN, L. & ZIEMKIEWICZ, P. (1997): Neutralization potential of overburden samples containing siderite. –J. Environ. Qual., 26, 673–681.
STARKEY, H.C., BLACKMON, P.D. & HAUFF, P.L. (1984): The routine mineralogical analysis of clay-bearing samples. -U.S.G.S. Bull., 1563, 1–32.
TESSIER, A., RAPIN, F. & CARIGNAN, R. (1985): Trace metals in oxic lake sediments: possible adsorption onto iron oxyhydroxides. -Geochim. Cosmochim. Acta, 49, 183-194.
THURMAN, E.M. (1986): Organic geochemistry of natural waters. Martinus Nijhoff/Dr W. Junk Publishers, Boston, 497 p.
TOMLJENOVIĆ, B. (2000): Zagorje–Mid–Transdanubian Zone.– In: PAMIĆ, J. & TOMLJENOVIĆ, B. (eds.): Vijesti.– Fieldtrip Guidebook. Proc. of the PANCARDI 2000, Dubrovnik, Croatia, 1–3 October, 2000, Zagreb, 37/2, 27–33.
TOMLJENOVIĆ, B. (2002): Strukturne karakteristike Medvednice i Samoborskog gorja [Structural characteristics of the Mts. Medvednica and the Samoborsko Gorje Mts. – in Croatian]. -Unpubl. PhD thesis, University of Zagreb, 208 p.
WU, J., WEST, L.J. & STEWART, D.I. (2002): Effect of humic substances on Cu(II) solubility in kaolin-sand soil. –J. Hazard. Mater., 94, 223-238.
BELAK, M., PAMIĆ, J., KOLAR-JURKOVŠEK, T., PECKAY, Z. & KARAN, D. (1995): Alpinski regionalnometamorfni kompleks Medvednice (sjeverozapadna Hrvatska) [Alpine regional metamorphic complex of the Medvednica Mt., NW Croatia – in Croatian]. -1. hrvatski geol. kongres, Zbornik radova, 1, 67-70, Zagreb.
BOROJEVIĆ ŠOŠTARIĆ, S. (2004): Geneza sideritno-baritno-polisulfidnih ležišta u paleozoiku Unutrašnjih Dinarida [Genesis of siderite–barite–polysulphide ore deposits within Palaeozoic of Internal Dinarides – in Croatian]. –Unpublished Masters thesis, University of Zagreb, 120 p.
DAVIS, J.A. (1982): Adsorption of natural dissolved organic matter at the oxide/water interface. -Geochim. Cosmochim. Acta, 46, 2381-2393.
ÐURÐANOVIĆ, Ž. (1973): O paleozoiku i trijasu Medvednice (Zagrebaèke gore) i područja Dvora na Uni na temelju konodonta [About the Paleozoic and the Triassic of Medvednica Mt. and the area near Dvor na Uni on the basis of conodonts– in Croatian]. -Geol. Vjesn., Zagreb, 25, 29-49.
DURN, G., MIKO, S., ČOVIĆ, M., BARUDŽIJA, U., Tadej, N., NAMJESNIK-DEJANOVIĆ; K. & PALINKAŠ, L. (1999): Distribution and behaviour of selected elements in soil developed over a historical Pb–Ag mining site at Sv. Jakob, Croatia. -J. Geochem. Explor., 67, 361–376.
FENG, X.H., ZHAI, L.M., TAN, W.F., LIU, F. & HE, J.Z. (2007): Adsorption and redox reactions of heavy metals on synthesized Mn oxide minerals. –Environ. Pollut.,147, 366-373.
FOLEY, N.K. (2002): Environmental geochemistry of platform carbonate-hosted sulphide deposits. http://pubs.usgs.gov/of/2002/of02-195/ChE.txt.
GUNDERSEN, P. & STEINNES, E. (2003): Influence of pH and TOC concentration on Cu, Zn, Cd, and Al speciation in rivers. -Water Res., 37, 307–318.
GUNGOR, E.B.O. & BEKBOLET, M. (2010): Zinc release by humic and fulvic acid as influenced by pH, complexation and DOC sorption. –Geoderma, 159,131–138.
HALAMIĆ, J., PEH, Z., BUKOVEC, D., MIKO, S. & GALOVIĆ, L. (2001): A factor model of the relationship between stream sediment geochemistry and adjacent drainage basin lithology, Medvednica Mt., Croatia. –Geol. Croat., 54, 37-51.
HALAMIĆ, J., GALOVIĆ, L. & ŠPARICA, M. (2003): Heavy metal (As, Cd, Cu, Hg, Pb and Zn) distribution in topsoil developed on alluvial sediments of the Drava and Sava rivers in NW Croatia. –Geol. Croat., 56, 215-232.
HEM, J.D. (1977.): Reactions of Metal-Ions at Surfaces of Hydrous Iron-Oxide. -Geochim. Cosmochim. Acta, 41, 527-538.
HERAK, M. (1956): Geologija Samoborskog gorja. –Acta geol., JAZU, Zagreb, I, 49–74.
HUANG, X., SILLANPÄÄ, M., GJESSING, E.T., PERÄNIEMI, S. & VOGT, R.D. (2010): Environmental impact of mining activities on the surface water quality in Tibet: Gyama valley. -Sci Total Environ., 408, 4177-4184.
JAMES, R.O. & MACNAUGHTON, M.G. (1977): The adsorption of aqueous heavy metals on inorganic minerals. –Geochim. Cosmochim. Acta, 41, 1549-1555.
MASCARO, I., BENVENUTI, M., CORSINI, F., COSTAGLIOLA, P., LATTANZI, P. PARRINI, P. & TANELLI, G. (2001): Mine wastes at the polymetallic deposit of Fenice Capanne (Southern Tuscany, Italy): Mineralogy, geochemistry and environmental impact. –Environ. Geol., 41, 417–429.
NAMJESNIK-DEJANOVIĆ, K. (1994): Distribucija teških metala u tlima grada Zagreba i njegove okolice [Distribution of heavy metals in the soils of Zagreb and its surrounding areas – in Croatian]. -Unpubl. master thesis, University of Zagreb, 208 p.
OG 77/98: Water classification act. Narodne novine (2008): Uredba o klasifikaciji voda. No 77.
OG 47/08: Regulation on health safety of drinking water. Narodne novine (2008): Pravilnik o zdravstvenoj ispravnosti vode za piće. No 47.
ÖZKARAOVA GUNGOR, E.B. & BEKBOLET, M. (2010) Zinc release by humic and fulvic acid as influenced by pH, complexation and DOC sorption. –Geoderma, 159,131–138.
PALINKAŠ, L., NAMJESNIK-DEJANOVIĆ, K., MIKO, S., DURN, G. & PIRC, S. (1996): Distribution of mercury, lead and cadmium in Zagreb city soils. –In: Richardson, M. (Ed.) Environmental xenobiotics, Taylor & Francis, London, 355-374.
PALINKAŠ, L., BOROJEVIĆ ŠOŠTARIĆ, S. & STRMIĆ PALINKAŠ, S. (2008): Metallogeny of the Northwestern and Central Dinarides and Southern Tisia. -Ore Geol. Rev., 34, 501-520.
PALINKAŠ, L., BOROJEVIĆ ŠOŠTARIĆ, S., STRMIĆ PALINKAŠ, S., PROCHASKA, W., SPANGENBERG, J., CUNA, S. & ŠINKOVEC, B. (2010): Permian–polysulphide-siderite–barite–haematite deposit Rude in Samoborska Gora Mts., Zagorje–Mid–Transdanubian zone of the Internal Dinarides. –Geol. Croat., 63, 93–115.
PAMIĆ, J. & TOMLJENOVIĆ, B. (1998): Basic geological data from the Croatian part of the Zagorje–Mid–Transdanubian Zone. –Acta Geol. Hungarica, 41, 389–400.
PEH, Z. (1992): Factor model of the geomorphological system of a part of Northwestern Croatia.- Geol. Croat., 45, 163-172.
PENG, J.-F., SONG, Y.-H., YUAN, P., CUI, X.-Y. & QIU, G.-L. (2009): The remediation of heavy metals contaminated sediment. -J. Hazard. Mater., 161, 633–640.
ROSE, A.W., DAHLBERG, E.C. & KEITH, M.L. (1970): A multiple regression technique for adjusting background values in stream sediment geochemistry. -Econ. Geol., 65, 156-165.
RYBICKA, E.H., CALMANO, W. & BREEGER, A. (1985): Heavy metals sorption/desorption on competing clay minerals; an experimental study. –Appl. Clay Sci., 9, 369-381.
ŠIKIĆ, K. (1995): Geološki vodič Medvednice.– Zagreb: Inst. geol.istraž., Zagreb, 199 p.
ŠIKIĆ, K., BASCH, O. & ŠIMUNIĆ, A. (1978): Osnovna geološka karta SFRJ 1:100 000. List Zagreb, L33–80 [Basic geological map of SFRY 1:100000, Zagreb sheet – in Croatian].– Inst. geol. istraž., Zagreb (1972), Sav. geol. zavod, Beograd.
ŠIKIĆ, K., BASCH, O. & ŠIMUNIĆ, A. (1979): Tumač osnovne geološke karte 1:100000, list Zagreb. –Sav. geol. zavod, Beograd, 81 p.
ŠINKOVEC, B. (1971): Geologija ležišta željezne i bakrene rude u Rudama kraj Samobora [Geology of iron and copper ore from Rude near Samobor – in Croatian]. –Geol. Vjesn., Zagreb, 24, 165–181.
ŠINKOVEC, B., PALINKAŠ, L. & DURN, G. (1988): Ore occurrences on Mt. Medvednica (in Croatian with English summary). -Geol. Vjesn., Zagreb, 41, 395–405.
SKOUSEN, J., RENTON, J., BROWN, H., EVANS, P., LEAVITT, B., BRADY, K., COHEN, L. & ZIEMKIEWICZ, P. (1997): Neutralization potential of overburden samples containing siderite. –J. Environ. Qual., 26, 673–681.
STARKEY, H.C., BLACKMON, P.D. & HAUFF, P.L. (1984): The routine mineralogical analysis of clay-bearing samples. -U.S.G.S. Bull., 1563, 1–32.
TESSIER, A., RAPIN, F. & CARIGNAN, R. (1985): Trace metals in oxic lake sediments: possible adsorption onto iron oxyhydroxides. -Geochim. Cosmochim. Acta, 49, 183-194.
THURMAN, E.M. (1986): Organic geochemistry of natural waters. Martinus Nijhoff/Dr W. Junk Publishers, Boston, 497 p.
TOMLJENOVIĆ, B. (2000): Zagorje–Mid–Transdanubian Zone.– In: PAMIĆ, J. & TOMLJENOVIĆ, B. (eds.): Vijesti.– Fieldtrip Guidebook. Proc. of the PANCARDI 2000, Dubrovnik, Croatia, 1–3 October, 2000, Zagreb, 37/2, 27–33.
TOMLJENOVIĆ, B. (2002): Strukturne karakteristike Medvednice i Samoborskog gorja [Structural characteristics of the Mts. Medvednica and the Samoborsko Gorje Mts. – in Croatian]. -Unpubl. PhD thesis, University of Zagreb, 208 p.
WU, J., WEST, L.J. & STEWART, D.I. (2002): Effect of humic substances on Cu(II) solubility in kaolin-sand soil. –J. Hazard. Mater., 94, 223-238.