Distribution of copper and zinc in the soil of an industrial zone in the city of Garešnica, Croatia
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Published:
Jun 20, 2009
Keywords:
urban soil, copper contamination, leaching, enrichment factors, Bakrotisak factory, Garešnica, Croatia
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Abstract
Soils from an industrial zone in Garešnica, Croatia have been analysed by EDXRF and XRD. In the area surrounding two adjacent factories named 'Bakrotisak' and 'Croatia Protekt', thirty soil sites (depth 5-15 cm) were sampled in December 2007, together with five soil sites from the forest (check samples) situated 0.5 km away. The locality was selected for its periodical, industrially induced environmental pollution which affects nearby streams and fish ponds, resulting in occasional fish kills in the region. Analysis included the determination of the soil mineralogy, total organic matter contents, cation exchange capacity, bulk multi-element composition and heavy metal levels in leachates (exchangeable fraction). Multi-element concentrations in the check samples constituted natural levels based on their perfect normal distributions. The Kruskal-Wallis test showed higher, statistically significant (P = 0.0005) concentrations of Cu in the soil surrounding 'Bakrotisak' compared to the check samples. Furthermore, leaching analysis confirmed the copper contamination of the 'Bakrotisak' soil by highly significant positive correlation (the Kendall's Tau correlation coefficient >0.99) between its extractable Cu and total Cu levels. Moreover, enrichment factors based on Al as a reference element were found to be >2 for approximately 50% samples of the 'Bakrotisak' soil, suggesting its moderate anthropogenic contamination.
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References
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KOVAČIĆ, M. & GRIZELJ, A. (2006):Provenance of the Upper Mio-cene clastic material in the southwestern part of the Pannonian Ba-sin.– Geol. Carpat., 57, 495−510.
KUO, S., HEILMAN, P.E. & BAKER, A.S. (1983): Distribution and forms of copper, zinc, iron, and manganese in soils near a copper smelter.− Soil Sci., 135, 101−109.
LI, J., XIE, Z.M., XU, J.M. & SUN, Y.F. (2006): Risk assessment for safety of soils and vegetables around a lead/zinc mine.– Environ. Geochem. Hlth., 28, 37−44. doi: 10.1007/s10653-005-9009-x
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LOUGHNAN, F.C. (1969): Chemical weathering of the silicate miner-als.– American Elsevier Publishing Company, New York, 154 p.MACKLIN, M.G. (1992): Metal contaminated soils and sediment: a ge-ographical perspective.– In: NEWSON, M.D. (ed.): Managing the human impact on the natural environment: patterns and processes. Belhaven Press, London, 172−195.
MARTLEY, E., GULSON, B., LOUIE, H., WU, M. & DI, P. (2004): Metal partitioning in soil profi les in the vicinity of an industrial complex, New South Wales, Australia.− Geochem.: Explor. Env., A4, 171−179. doi: 10.1144/1467-7873/03-030
MATSCHULLAT, J., OTTENSTEIN, R. & REIMANN, C. (2000): Ge-ochemical background – can we calculate it?– Environ. Geol., 39/9, 990–1000. doi: 10.1007/s002549900084
MERRINGTON, G. & ALLOWAY, B.J. (1994): The fl ux of Cd, Cu, Pb and Zn in mining polluted soils.− Water Air Soil Poll., 73, 333−344. doi: 10.1007/BF00477997
MIKO, S., HALAMIĆ, J., PEH, Z. & GALOVIĆ, L. (2001): Geochem-ical baseline mapping of soils developed on diverse bedrock from two regions in Croatia.– Geol. Croat., 54/1, 53−118.
OREŠČANIN, V., KATUNAR, A., KUTLE, A. & VALKOVIĆ, V. (2003): Heavy metals in soil, grape, and wine.– J. Trace Micro-probe T., 21, 171–180. doi: 10.1081/TMA-120017912
PROHIĆ, E., MIKO, S. & PEH, Z. (1995): Normalization and trace ele-ment contamination of soils in a karstic polje – an example from the Sinjsko Polje, Croatia.– Geol. Croat., 48/1, 67−86.
REIMANN, C. & FILZMOSER, P. (2000): Normal and lognormal data distribution in geochemistry: death of a myth. Consequences for the statistical treatment of geochemical and environmental data.– Environ. Geol., 39/9, 1001–1014. doi: 10.1007/s002549900081
REIMANN, C., FILZMOSER, P. & GARRETT, R.G. (2005): Back-ground and threshold: critical comparison of methods of determi-nation.– Sci. Tot. Env., 346, 1−16. doi: 10.1016/j.scitotenv.2004. 11.023
REIMANN, C. & GARRETT, R.G. (2005): Geochemical background – concept and reality.– Sci. Tot. Env., 350, 12–27. doi: 10.1016/j.scitotenv.2005.01.047
SALOMONS, W. & FÖRSTNER, U. (1984): Metals in the hydrocy-cle.– Springer-Verlag., Berlin-Heidelberg, 349 p.
SPATARI, S., BERTRAM, M., FUSE, K., GRAEDEL, T.E. & RECH-BERGER, H. (2002): The contemporary European copper cycle: 1 year stocks and fl ows.– Ecol. Econ., 42, 27−42. doi: 10.1016/S0921- 8009(02)00103-9
ŠKORIĆ, A. (1986): Postanak, razvoj i sistematika tla [Genesis, devel-opment, and systematics of soils− in Croatian].– Fakultet poljo-privrednih znanosti Sveučilišta u Zagrebu, Zagreb, 172 p.
ŠPOLJAR, A. (1999): FAO klasifi kacija s bazom podataka za pedološku kartu Republike Hrvatske sitnog mjerila [FAO classifi cation with database of pedologic map of Croatia in small scale− in Croatian].– Unpubl. MSc. Thesis, University of Zagreb, 75 p.
THORNTON, I. (1990): Soil contamination in urban areas.– Palaeoge-ogr. Palaeoclimatol. Palaeoecol., 82, 121−140.
VAN OLPHEN, H. & FRIPIAT, J.J. (1979): Data handbook for clay ma-terials and other non-metallic minerals.– Pergamon Press, Oxford, 346 p.WARREN, R.S. & BIRCH, P. (1987): Heavy metal levels in atmosphe-ric particles, roadside dust and soil along a major urban highway.– Sci. Total. Environ., 59, 253–256. doi: 10.1016/0048-9697(87) 90446-3
YONG, R.N. & WARKENTIN, B.P. (1975): Soil properties and behav-iour.– Elsevier, Amsterdam, 449 p.
AMMANN, L., BERGAYA, F. & LAGALY, G. (2005): Determination of the cation exchange capacity of clays with cooper complexes revisited.− Clay Min., 40, 441−453. doi: 10.1180/0009855054040182
BERTRAM, M., GRAEDEL, T.E., RECHBERGER, H. & SPATARI, S. (2002): The contemporary European copper cycle: waste manage-ment subsystem.– Ecol. Econ., 42, 43–57. PII: S0921-8009(02) 00100-3
CRNKO, J. (1998): Vodič geološke ekskurzije na Moslavačku goru [Cro-atian Geological Society Excursion Guide Book for Moslavačka Gora – in Croatian].– Hrvatsko geološko društvo, Zagreb, 85 p.
DASKALAKIS, K.D. & O’CONNOR, T.P. (1995): Normalization and elemental sediment contamination in the Coastal United States.– Env. Sci. Technol., 29/2, 470−477. doi: 10.1021/es00002a024
FÖRSTNER, U. & WITTMANN, G.T.W. (1979): Metal pollution in the aquatic environment.– Springer-Verlag, Berlin, Heidelberg, New York, 486 p.GLEIT, A. (1985): Estimation for small normal data sets with detection limits.– Environ. Sci. Technol., 19, 1201–1206. doi: 10.1021/es00142a011
GOLCHERT, B., LANDSBERGER, S. & HOPKE, P.K. (1991): Deter-mination of heavy metals in the Rock River (Illinois) through the analysis of sediments.– J. Radioan. Nucl. Ch.-Ar., 148/2, 319−337. doi: 10.1007/BF02060365
GRAEDEL, T.E., BERTRAM, M., FUSE, K., GORDON, R.B., LIFSET, R., RECHBERGER, H. & SPATARI, S. (2002): The contemporary European copper cycle: The characterization of technological cop-per cycles.– Ecol. Econ., 42, 9–26. doi: 10.1016/S0921-8009(02) 00101-5
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., 56/2, 215−232.
HANSON, P.J., EVANS, D.W., COLBY, D.R. & ZDANOWICZ, V.S. (1993): Assessment of elemental contamination in estuarine and coastal environments based on geochemical and statistical modeling of sediments.– Marine Environ. Res., 36/4, 237−266. doi: 10.1016/ 0141-1136(93)90091-D
HU, N., LI, Z., HUANG, P. & TAO, C. (2006): Distribution and mobil-ity of metals in agricultural soils near a copper smelter in South China.– Environ. Geochem. Hlth., 28, 19–26. doi: 10.1007/s10653-005-9007-z
JURAK, V., PFAFF, S., HORVAT, K. & KRKLEC, N. (2006): Provjera hipoteze o homogenosti geotehničkih sredina na lokaciji 'Čađare' u Kutini [Verifi cation of the hypothesis regarding the homogeneity of geotechnical mediums at the 'Soot factory / Čađara' location in Kutina – in Croatian].– Rudarsko-geološko-naftni zbornik, Zagreb, 18, 29−41.
KOROLIJA, B. & CRNKO, J. (1985): Osnovna geološka karta SFRJ 1:100000 list Bjelovar, L 33−82 [Basic Geological Map of SFRY 1:100000, Bjelovar sheet – in Croatian].– Geološki zavod Zagreb, Savezni geološki zavod, Beograd.
KOROLIJA, B., VRAGOVIĆ, M., CRNKO, J. & MAMUŽIĆ, P. (1986): Osnovna geološka karta SFRJ 1:100000. Tumač za list Bjelovar L 33−82 [Basic Geological Map of SFRY 1:100000, Geology of the Bjelovar sheet – in Croatian].– Geološki zavod Zagreb, Savezni geološki zavod, Beograd, 45 p.
KOVAČIĆ, M. & GRIZELJ, A. (2006):Provenance of the Upper Mio-cene clastic material in the southwestern part of the Pannonian Ba-sin.– Geol. Carpat., 57, 495−510.
KUO, S., HEILMAN, P.E. & BAKER, A.S. (1983): Distribution and forms of copper, zinc, iron, and manganese in soils near a copper smelter.− Soil Sci., 135, 101−109.
LI, J., XIE, Z.M., XU, J.M. & SUN, Y.F. (2006): Risk assessment for safety of soils and vegetables around a lead/zinc mine.– Environ. Geochem. Hlth., 28, 37−44. doi: 10.1007/s10653-005-9009-x
LI, X. & THORNTON, I. (2001): Chemical partitioning of trace and major elements in soils contaminated by mining and smelting acti-vities.− Applied Geochem., 16, 1693−1706. doi: 10.1016/S0883-2927 (01)00065-8
LOUGHNAN, F.C. (1969): Chemical weathering of the silicate miner-als.– American Elsevier Publishing Company, New York, 154 p.MACKLIN, M.G. (1992): Metal contaminated soils and sediment: a ge-ographical perspective.– In: NEWSON, M.D. (ed.): Managing the human impact on the natural environment: patterns and processes. Belhaven Press, London, 172−195.
MARTLEY, E., GULSON, B., LOUIE, H., WU, M. & DI, P. (2004): Metal partitioning in soil profi les in the vicinity of an industrial complex, New South Wales, Australia.− Geochem.: Explor. Env., A4, 171−179. doi: 10.1144/1467-7873/03-030
MATSCHULLAT, J., OTTENSTEIN, R. & REIMANN, C. (2000): Ge-ochemical background – can we calculate it?– Environ. Geol., 39/9, 990–1000. doi: 10.1007/s002549900084
MERRINGTON, G. & ALLOWAY, B.J. (1994): The fl ux of Cd, Cu, Pb and Zn in mining polluted soils.− Water Air Soil Poll., 73, 333−344. doi: 10.1007/BF00477997
MIKO, S., HALAMIĆ, J., PEH, Z. & GALOVIĆ, L. (2001): Geochem-ical baseline mapping of soils developed on diverse bedrock from two regions in Croatia.– Geol. Croat., 54/1, 53−118.
OREŠČANIN, V., KATUNAR, A., KUTLE, A. & VALKOVIĆ, V. (2003): Heavy metals in soil, grape, and wine.– J. Trace Micro-probe T., 21, 171–180. doi: 10.1081/TMA-120017912
PROHIĆ, E., MIKO, S. & PEH, Z. (1995): Normalization and trace ele-ment contamination of soils in a karstic polje – an example from the Sinjsko Polje, Croatia.– Geol. Croat., 48/1, 67−86.
REIMANN, C. & FILZMOSER, P. (2000): Normal and lognormal data distribution in geochemistry: death of a myth. Consequences for the statistical treatment of geochemical and environmental data.– Environ. Geol., 39/9, 1001–1014. doi: 10.1007/s002549900081
REIMANN, C., FILZMOSER, P. & GARRETT, R.G. (2005): Back-ground and threshold: critical comparison of methods of determi-nation.– Sci. Tot. Env., 346, 1−16. doi: 10.1016/j.scitotenv.2004. 11.023
REIMANN, C. & GARRETT, R.G. (2005): Geochemical background – concept and reality.– Sci. Tot. Env., 350, 12–27. doi: 10.1016/j.scitotenv.2005.01.047
SALOMONS, W. & FÖRSTNER, U. (1984): Metals in the hydrocy-cle.– Springer-Verlag., Berlin-Heidelberg, 349 p.
SPATARI, S., BERTRAM, M., FUSE, K., GRAEDEL, T.E. & RECH-BERGER, H. (2002): The contemporary European copper cycle: 1 year stocks and fl ows.– Ecol. Econ., 42, 27−42. doi: 10.1016/S0921- 8009(02)00103-9
ŠKORIĆ, A. (1986): Postanak, razvoj i sistematika tla [Genesis, devel-opment, and systematics of soils− in Croatian].– Fakultet poljo-privrednih znanosti Sveučilišta u Zagrebu, Zagreb, 172 p.
ŠPOLJAR, A. (1999): FAO klasifi kacija s bazom podataka za pedološku kartu Republike Hrvatske sitnog mjerila [FAO classifi cation with database of pedologic map of Croatia in small scale− in Croatian].– Unpubl. MSc. Thesis, University of Zagreb, 75 p.
THORNTON, I. (1990): Soil contamination in urban areas.– Palaeoge-ogr. Palaeoclimatol. Palaeoecol., 82, 121−140.
VAN OLPHEN, H. & FRIPIAT, J.J. (1979): Data handbook for clay ma-terials and other non-metallic minerals.– Pergamon Press, Oxford, 346 p.WARREN, R.S. & BIRCH, P. (1987): Heavy metal levels in atmosphe-ric particles, roadside dust and soil along a major urban highway.– Sci. Total. Environ., 59, 253–256. doi: 10.1016/0048-9697(87) 90446-3
YONG, R.N. & WARKENTIN, B.P. (1975): Soil properties and behav-iour.– Elsevier, Amsterdam, 449 p.