Comparison of urban and rural soils based on speciation of heavy metals by BCR sequential extraction procedure: A case study in the historical and industrial city of Sisak, Croatia
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Jun 14, 2023
Keywords:
SEP, potentially toxic elements, soil profiles, anthropogenic influences, risk assessment
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Abstract
Within the framework of the pan-European project “URban GEochemistry (URGE) in Europe – Soil, children, health”, pedological and geochemical investigations of the soils of the city of Sisak and its adjacent surroundings were carried out, and three urban and two rural soil profiles were examined. The mineralogical composition and concentration of selected potentially toxic elements (PTEs) Cr, Cu, Ni, Pb and Zn in the soil were determined. The Community Reference Bureau of Reference (BCR) sequential extraction procedure (SEP) of these PTEs was undertaken and the potential risk to human health and the environment was assessed.
The concentrations of Cr and Ni are generally similar in urban and rural soil profiles, while the concentrations of Cu, Pb and Zn in soil horizons/layers are higher in urban profiles. The extracted fractions of PTEs gave the following general distribution: in urban soil profiles residual (RES) > reducible (ORG) or oxidisable (FEMN) > exchangeable (CARB), except for Cu where ORG > RES > FEMN > CARB, while in rural soil profiles RES > FEMN or ORG > CARB, except for Pb where FEMN > RES or ORG > CARB.
The differences between soils in urban and rural profiles depend mainly on the historical land use, i.e. on the duration and intensity of anthropogenic influences on the soil and, to a lesser extent, on the geogenic origin of the parent material and the pedogenic processes. The studied elements in the urban soil profiles are predominantly of anthropogenic origin, indicating a possible influence of the ancient settlements of Segestica and Siscia and of heavy industry in the 20th century. The anthropogenic influences on the rural profiles are low and geogenic influences dominate.
Risks to the environment were assessed in the soil profiles based on PTE concentrations in the CARB fraction and the sum of the CARB, ORG and FEMN fractions from BCR SEP. All calculated risks to human health and the environment were rated as no-risk, very low risk and low risk.
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References
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ETTLER, V., VANĚK, A., MIHALJEVIČ, M. & BEZDIČKA, P. (2005): Contrasting lead speciation in forest and tilled soils heavily polluted by lead metallurgy.– Chemosphere, 58, 1449–1459. doi: 10.1016/j.chemosphere.2004.09.084
EUROPEAN COMMISSION (2001): Report 19775 EN of the European Commission: The certification of the extractable contents (mass fractions) of Cd, Cr, Cu, Ni, Pb and Zn in freshwater sediment following a sequential extraction procedure BCR-701.– Competitive and Sustainable Growth.
GLEYZES, CH., TELLIER, S. & ASTRUC, M. (2002): Fractionation studies of trace elements in contaminated soils and sediments: a review of sequential extraction procedures.– Trends in analytical chemistry, 21, No. 6 + 7, 451–467. doi: 10.1016/S0165-9936(02)00603-9
GREINERT, A. (2015): The heterogeneity of urban soils in the light of their properties.– J. Soils Sediments, 15/8, 1725–1737. doi: 10.1007/s11368-014-1054-6.
GREINERT, A. & KOSTECKI, J. (2019): Anthropogenic Materials as Bedrock of Urban Technosols.– In: VASENEV, V., DOVLETYAROVA, E., CHENG, Z., PROKOF’EVA, T., MOREL, J. & ANANYEVA, N. (eds.): Urbanization: Challenge
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HUSNJAK, S., RUBINIĆ, V., HALAMIĆ, J., ŠORŠA, A. & VRBEK, B. (2018): Characteristics and classification of three urban soils in the Sisak city, Croatia.– Agriculturae Conspectus Scientificus, 83/3, 231–238.
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KHADHAR, S., SDIRI, A., CHEKIRBEN, A., AZOUZI, R. & CHAREF, A. (2020): Integration of sequential extraction, chemical analysis and statistical tools for the availability risk assessment of heavy metals in sludge amended soils.– Environ. Pollut, 263. doi: 10.1016/j.envpol.2020.114543
LEHMANN, A. & STAHR, K. (2007): Nature and significance of anthropogenic urban soils.– J. Soils Sediments, 7, 247–260. doi: 10.1065/jss2007.06.235
LISAC, I. & HERIĆ-NEKIĆ, S. (1995): Contribution to the knowledge of the climate of Sisak.– Croatian Meteorological Journal, 30, 79–99.
LIU, J., CHEN, Y., WANG, J., QI, J. WANG, C., LIPPOLD, H. & LIPPMANN-PIPKE, J. (2010): Factor analysis and sequential extraction unveil geochemical processes relevant for trace metal distributions in fluvial sediments of a pyrite mining area, China.– Carbonates and Evaporites, 25, 51–63. doi: 10.1007/s13146-010-0007-4
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MIKO, S., DURN, G., ADAMCOVÀ, R., ČOVIĆ, M., DUBIKOVÀ, M., SKALSKÝ, R., KAPELJ, S. & OTTNER, F. (2003): Heavy metal distribution in karst soil from Croatia and Slovakia.– Environmental Geology, 45, 262–272. doi: 10.1007/s00254-003-0878-y
MOORE D.M. & REYNOLDS R.C. JR. (1997): X-ray diffraction and the identification and analysis of clay Minerals.– Oxford University Press, Oxford, 378 p.
NIEUWENHUIZE, J., POLEY-VOS, C.H., VAN DER AKKER, A.H. & VAN DELFT, W. (1991): Comparison of microwave and conventional extraction techniques for the determination of metals in soils, sediments and sludge samples by atomic spectrometry.– Analyst, 116, 347–351. doi: 10.1039/an9911600347
O’RIORDAN, R., DAVIES, J., STEVENS, C., QUINTON, J.N. & BOYKO, CH. (2021): The ecosystem services of urban soils: A review.– Geoderma 395, 115076. doi: 10.1016/j.geoderma.2021.115076
PIKIJA, M. (1987a): Osnovna geološka karta SFRJ 1:100 000, list Sisak [Basic Geological Map of the SFRJ 1:100,000, Sisak sheet – in Croatian].– Geol. Zavod Zagreb, Savezni geol. Zavod, Beograd.
PIKIJA, M. (1987b): Osnovna geološka karta SFRJ 1:100 000. Tumač za list Sisak [Basic Geological Map of the SFRJ 1:100,000, Explantory notes for Sisak sheet – in Croatian with English summary].– Geol. Zavod Zagreb, Savezni geol. Zavod, Beograd, 55 p.
POUYAT, R.V., SZLAVECZ, K., YESILONIS, I.D., GROFFMAN, P.M. & SCHWARZ, K. (2010): Chemical, Physical and Biological Characteristics of Urban Soils.– In: AITKENHEAD-PETERSON, J. & VOLDER, A. (eds.): Agronomy Monograph 55, Urban Ecosystem Ecology. American Society of Agronomy, Crop Science Society of America, Soil Science Society of America, Madison, USA, 119–155. doi: 10.2134/agronmonogr55.c7
PUEYO, M., RAURET, G., LÜCK, A.D., YLI-HALLA, B.M., MUNTAU, C.H., QUEVAUVILLERE, D.PH. & LÓPEZ-SÁNCHEZ, J.F. (2001): Certification of the extractable contents of Cd, Cr, Cu, Ni, Pb and Zn in a freshwater sediment following a collaboratively tested and optimised three-step sequential extraction procedure.– J. Environ. Monit., 243–250. doi: 10.1039/b010235k
RAPANAT, S., SALMINEN, R., TARVAINEN, T., KRČMOVÀ, K. & CVEČKOVÀ (2008): Application of a risk assessment method to Europe-wide geochemical baseline data.– Geochemistry: Exploration, Environment, Analysis, 8, 291–299. doi: 10.1144/1467-7873/08-176
RATH, P., PANDA, U.C., BHATTA, D. & SAHU, K.C. (2009): Use of sequential leaching, mineralogy, morphology, and multivariate statistical technique for quantifying metal pollution in highly polluted aquatic sediments – A case study: Brahmani and Nandira Rivers, India.– Journal of Hazardous Materials, 163, 632–644. doi: 10.1016/j.jhazmat.2008.07.048
REIMANN, C., FILZMOSER, P., GARRET, R.G. & DUTTER, R. (2008): Statistical Data Analysis Explained.– John Wiley and Sons, Ltd. SCHULTZ, L.G. (1964): Quantitative interpretation of mineralogical composition from X-ray and chemical data for the Pierre Shale.– U.S. Geological Survey Proffesional Paper 391-C, 31 p.
SLUKAN ALTIĆ, M. (2004): Povijesni atlas gradova: Sisak [Historical – Towns’ Atlas: Sisak – in Croatian].– Sisak State Archives & Croatian State Archives, Zagreb, 241 p.
SOBOCKÁ, J. (2003): Urban soils vs. anthropogenic soils, their differentiation and classification.– Final Program and Abstracts Book, SUITMA Int. Conf., July, 9–11. 2003, Nancy, France, 41–42.
ŠORŠA, A. (2014): Urban geochemistry of the potentially toxic elements in the soils of the Sisak city and its surroundings.– Unpubl. PhD Thesis, Faculty of Mining, Geology and Petroleum Engineering, University of Zagreb, 308 p.
ŠORŠA, A. & HALAMIĆ, J. (2014): Geochemical Atlas of Sisak.– Public Library Vlado Gotovac Sisak, City Museum Sisak and Croatian Geological Survey, Sisak-Zagreb, 200 p.
ŠORŠA, A., DURN, G., HALAMIĆ, J., HUSNJAK, S., GARAŠIĆ, V. & MILEUSNIĆ, M. (2017): Urban geochemistry: Sisak in Croatia, a long-lasting historical, urban and industrial city.– Geochemistry: Exploration, Environment, Analysis, 17/2, 159–163. doi: 10.1144/geochem2015-395
ŠORŠA, A., PEH, Z. & HALAMIĆ, J. (2018): Geochemical mapping the urban and industrial legacy of Sisak, Croatia, using discriminant function analysis of topsoil chemical data.– Journal of Geochemical Exploration, 187, 155–167. doi: 10.1016/j.gexplo.2017.07.014
STARKEY H.C., BLACKMON P.D. & HAUFF P.L. (1984): The Routine Mineralogical Analysis of Clay-Bearing Samples. – U.S. Geological Survey Bulletin 1563, 31 p.
TESSIER, A., CAMPBELL, P.G.C. & BISSON, M. (1979): Sequential Extraction Procedure for the Speciation of Particulate Trace Metals.– Analytical Chemistry, 51/7, 844–851. doi: 10.1021/ac50043a017
URE, A.M., QUEVAUVILLER, P.H., MUNTAU, H. & GRIEPNIK, B. (1993): Speciation of heavy metals in soils and sediments. An account of the improvement and harmonization of extraction techniques undertaken under the auspices of the BCR of the commission of the European communities.– International Journal of Environmental
Analytical Chemistry, 51, 135–151. doi: 10.1080/03067319308027619
ZIMMERMAN, A.J. & WEINDORF, D.C. (2010): Heavy Metal and Trace Metal Analysis in Soil by Sequential Extraction: A Review of Procedures.– Hindawi Publishing Corporation, International Journal of Analytical Chemistry, 387803. doi: 10.1155/2010/387803
DAVIDSON, C.M., THOMAS, R.P., McVEY, S.E., PERALA, R., LITTLEJOHN, D. & URE, A.M. (1994): Evaluation of a sequential extraction procedure for the speciation of heavy metals in sediments.– Anal. Chim. Acta, 291, 277–286. doi: 10.1016/0003-2670(94)80023-5
ETTLER, V., VANĚK, A., MIHALJEVIČ, M. & BEZDIČKA, P. (2005): Contrasting lead speciation in forest and tilled soils heavily polluted by lead metallurgy.– Chemosphere, 58, 1449–1459. doi: 10.1016/j.chemosphere.2004.09.084
EUROPEAN COMMISSION (2001): Report 19775 EN of the European Commission: The certification of the extractable contents (mass fractions) of Cd, Cr, Cu, Ni, Pb and Zn in freshwater sediment following a sequential extraction procedure BCR-701.– Competitive and Sustainable Growth.
GLEYZES, CH., TELLIER, S. & ASTRUC, M. (2002): Fractionation studies of trace elements in contaminated soils and sediments: a review of sequential extraction procedures.– Trends in analytical chemistry, 21, No. 6 + 7, 451–467. doi: 10.1016/S0165-9936(02)00603-9
GREINERT, A. (2015): The heterogeneity of urban soils in the light of their properties.– J. Soils Sediments, 15/8, 1725–1737. doi: 10.1007/s11368-014-1054-6.
GREINERT, A. & KOSTECKI, J. (2019): Anthropogenic Materials as Bedrock of Urban Technosols.– In: VASENEV, V., DOVLETYAROVA, E., CHENG, Z., PROKOF’EVA, T., MOREL, J. & ANANYEVA, N. (eds.): Urbanization: Challenge
and Opportunity for Soil Functions and Ecosystem Services. Proceedings of the 9th SUITMA 2017. Springer Geography, 11–20. doi: 10.1007/978-3-319-89602-1_3.
KAMINSKI-KIRŠ, N. (2002): Generalni urbanistički plan grada Siska - I dio [General urban plan of the city of Sisak – Part I – in Croatian].– CPA Centar za prostorno uređenje i arhitekturu d.o.o. Zagreb, 73 p.
HOOKER, P.J. & NATHANAIL, C.P. (2006): Risk-based characterisation of lead in urban soils.– Chem. Geol., 226, 340–351. doi: 10.1016/j.chemgeo.2005.09.028
HUSNJAK, S. (2012): Kompilirana pedološka karta grada Siska i okolice [Compiled pedological map of the city of Sisak and its surroundings – in Croatian].– Unpubl. report, Archive of the Croatian Geological Survey, Zagreb.
HUSNJAK, S. (2014): Sistematika tla Hrvatske [Soil systematics of Croatia – in Croatian].– Hrvatska sveučilišna naklada, Zagreb, 375 p.
HUSNJAK, S., RUBINIĆ, V., HALAMIĆ, J., ŠORŠA, A. & VRBEK, B. (2018): Characteristics and classification of three urban soils in the Sisak city, Croatia.– Agriculturae Conspectus Scientificus, 83/3, 231–238.
IUSS Working Group WRB (2014): World reference base for soil resources 2014.– World Soil Resources Reports, No. 106, FAO, Rome.
KHADHAR, S., SDIRI, A., CHEKIRBEN, A., AZOUZI, R. & CHAREF, A. (2020): Integration of sequential extraction, chemical analysis and statistical tools for the availability risk assessment of heavy metals in sludge amended soils.– Environ. Pollut, 263. doi: 10.1016/j.envpol.2020.114543
LEHMANN, A. & STAHR, K. (2007): Nature and significance of anthropogenic urban soils.– J. Soils Sediments, 7, 247–260. doi: 10.1065/jss2007.06.235
LISAC, I. & HERIĆ-NEKIĆ, S. (1995): Contribution to the knowledge of the climate of Sisak.– Croatian Meteorological Journal, 30, 79–99.
LIU, J., CHEN, Y., WANG, J., QI, J. WANG, C., LIPPOLD, H. & LIPPMANN-PIPKE, J. (2010): Factor analysis and sequential extraction unveil geochemical processes relevant for trace metal distributions in fluvial sediments of a pyrite mining area, China.– Carbonates and Evaporites, 25, 51–63. doi: 10.1007/s13146-010-0007-4
McGRATH, S.P. (1997): Chromium and Nickel.– In: ALLOWAY, B.J. (ed.): Heavy Metals in Soils.– Blackie Academic and Professional, London, 368 p.
MESIĆ, H., ČIDIĆ, A., DOMINIKOVIĆ ALAVANJA, S., KISIĆ, I., BAŠIĆ, F., ZGORELEC, Ž., HUSNJAK, S., ROMIĆ, D., KOMESAROVIĆ, B., KLAIĆ, D., PERNAR, N., BAKŠIĆ, D., VRBEK, B., PILAŠ, I., POTOČIĆ, N., SELETKOVIĆ, I., DURN, G., MILEUSNIĆ, M., NAKIĆ, Z. & MIKO, S. (2008): Izrada programa trajnog motrenja tala Hrvatske s pilot projektom LIFE05 TCY/CRO 000105.– In: KUČAR DRAGIČEVIĆ, S. (ed.): Program trajnog motrenja tala Hrvatske [in Croatian], Croatian Environmental Agency, Zagreb, 131 p.
MIKO, S., DURN, G., ADAMCOVÀ, R., ČOVIĆ, M., DUBIKOVÀ, M., SKALSKÝ, R., KAPELJ, S. & OTTNER, F. (2003): Heavy metal distribution in karst soil from Croatia and Slovakia.– Environmental Geology, 45, 262–272. doi: 10.1007/s00254-003-0878-y
MOORE D.M. & REYNOLDS R.C. JR. (1997): X-ray diffraction and the identification and analysis of clay Minerals.– Oxford University Press, Oxford, 378 p.
NIEUWENHUIZE, J., POLEY-VOS, C.H., VAN DER AKKER, A.H. & VAN DELFT, W. (1991): Comparison of microwave and conventional extraction techniques for the determination of metals in soils, sediments and sludge samples by atomic spectrometry.– Analyst, 116, 347–351. doi: 10.1039/an9911600347
O’RIORDAN, R., DAVIES, J., STEVENS, C., QUINTON, J.N. & BOYKO, CH. (2021): The ecosystem services of urban soils: A review.– Geoderma 395, 115076. doi: 10.1016/j.geoderma.2021.115076
PIKIJA, M. (1987a): Osnovna geološka karta SFRJ 1:100 000, list Sisak [Basic Geological Map of the SFRJ 1:100,000, Sisak sheet – in Croatian].– Geol. Zavod Zagreb, Savezni geol. Zavod, Beograd.
PIKIJA, M. (1987b): Osnovna geološka karta SFRJ 1:100 000. Tumač za list Sisak [Basic Geological Map of the SFRJ 1:100,000, Explantory notes for Sisak sheet – in Croatian with English summary].– Geol. Zavod Zagreb, Savezni geol. Zavod, Beograd, 55 p.
POUYAT, R.V., SZLAVECZ, K., YESILONIS, I.D., GROFFMAN, P.M. & SCHWARZ, K. (2010): Chemical, Physical and Biological Characteristics of Urban Soils.– In: AITKENHEAD-PETERSON, J. & VOLDER, A. (eds.): Agronomy Monograph 55, Urban Ecosystem Ecology. American Society of Agronomy, Crop Science Society of America, Soil Science Society of America, Madison, USA, 119–155. doi: 10.2134/agronmonogr55.c7
PUEYO, M., RAURET, G., LÜCK, A.D., YLI-HALLA, B.M., MUNTAU, C.H., QUEVAUVILLERE, D.PH. & LÓPEZ-SÁNCHEZ, J.F. (2001): Certification of the extractable contents of Cd, Cr, Cu, Ni, Pb and Zn in a freshwater sediment following a collaboratively tested and optimised three-step sequential extraction procedure.– J. Environ. Monit., 243–250. doi: 10.1039/b010235k
RAPANAT, S., SALMINEN, R., TARVAINEN, T., KRČMOVÀ, K. & CVEČKOVÀ (2008): Application of a risk assessment method to Europe-wide geochemical baseline data.– Geochemistry: Exploration, Environment, Analysis, 8, 291–299. doi: 10.1144/1467-7873/08-176
RATH, P., PANDA, U.C., BHATTA, D. & SAHU, K.C. (2009): Use of sequential leaching, mineralogy, morphology, and multivariate statistical technique for quantifying metal pollution in highly polluted aquatic sediments – A case study: Brahmani and Nandira Rivers, India.– Journal of Hazardous Materials, 163, 632–644. doi: 10.1016/j.jhazmat.2008.07.048
REIMANN, C., FILZMOSER, P., GARRET, R.G. & DUTTER, R. (2008): Statistical Data Analysis Explained.– John Wiley and Sons, Ltd. SCHULTZ, L.G. (1964): Quantitative interpretation of mineralogical composition from X-ray and chemical data for the Pierre Shale.– U.S. Geological Survey Proffesional Paper 391-C, 31 p.
SLUKAN ALTIĆ, M. (2004): Povijesni atlas gradova: Sisak [Historical – Towns’ Atlas: Sisak – in Croatian].– Sisak State Archives & Croatian State Archives, Zagreb, 241 p.
SOBOCKÁ, J. (2003): Urban soils vs. anthropogenic soils, their differentiation and classification.– Final Program and Abstracts Book, SUITMA Int. Conf., July, 9–11. 2003, Nancy, France, 41–42.
ŠORŠA, A. (2014): Urban geochemistry of the potentially toxic elements in the soils of the Sisak city and its surroundings.– Unpubl. PhD Thesis, Faculty of Mining, Geology and Petroleum Engineering, University of Zagreb, 308 p.
ŠORŠA, A. & HALAMIĆ, J. (2014): Geochemical Atlas of Sisak.– Public Library Vlado Gotovac Sisak, City Museum Sisak and Croatian Geological Survey, Sisak-Zagreb, 200 p.
ŠORŠA, A., DURN, G., HALAMIĆ, J., HUSNJAK, S., GARAŠIĆ, V. & MILEUSNIĆ, M. (2017): Urban geochemistry: Sisak in Croatia, a long-lasting historical, urban and industrial city.– Geochemistry: Exploration, Environment, Analysis, 17/2, 159–163. doi: 10.1144/geochem2015-395
ŠORŠA, A., PEH, Z. & HALAMIĆ, J. (2018): Geochemical mapping the urban and industrial legacy of Sisak, Croatia, using discriminant function analysis of topsoil chemical data.– Journal of Geochemical Exploration, 187, 155–167. doi: 10.1016/j.gexplo.2017.07.014
STARKEY H.C., BLACKMON P.D. & HAUFF P.L. (1984): The Routine Mineralogical Analysis of Clay-Bearing Samples. – U.S. Geological Survey Bulletin 1563, 31 p.
TESSIER, A., CAMPBELL, P.G.C. & BISSON, M. (1979): Sequential Extraction Procedure for the Speciation of Particulate Trace Metals.– Analytical Chemistry, 51/7, 844–851. doi: 10.1021/ac50043a017
URE, A.M., QUEVAUVILLER, P.H., MUNTAU, H. & GRIEPNIK, B. (1993): Speciation of heavy metals in soils and sediments. An account of the improvement and harmonization of extraction techniques undertaken under the auspices of the BCR of the commission of the European communities.– International Journal of Environmental
Analytical Chemistry, 51, 135–151. doi: 10.1080/03067319308027619
ZIMMERMAN, A.J. & WEINDORF, D.C. (2010): Heavy Metal and Trace Metal Analysis in Soil by Sequential Extraction: A Review of Procedures.– Hindawi Publishing Corporation, International Journal of Analytical Chemistry, 387803. doi: 10.1155/2010/387803