Abstract
Purpose
Rare earth elements (REE) are generally considered immobile and therefore suitable as provenance proxies. In the fluvial environment, however, several non-provenance factors may affect their content and obscure the accurate identification of sediment sources. This study, therefore, focuses on separating the lithological signal from the influence of anthropogenic activity and hydrodynamic sorting on REE geochemistry of fine-grained sediments. The study area comprises the upper catchment of the Sava River, the largest Danube tributary.
Materials and methods
The samples were characterised with respect to their mineralogical, granulometric and geochemical composition. The main factors governing the REE distribution were unravelled by the combined use of statistics (multidimensional scaling — MDS) and element ratios.
Results and discussion
Mineralogical analysis showed the dominance of carbonates in the upper reaches, while detritus, rich in aluminosilicates and quartz, predominated in other parts of the basin. Concentrations of REE ranged from 28.6 to 197 mg kg−1 in the Sava River and from 77.6 to 236 mg kg−1 in tributaries. Grain size changes due to hydrodynamic sorting influenced REE content more than lithology in the Sava River. Tributaries were more affected by the interaction between source lithology and anthropogenic activities, of which agriculture was the most important. Elemental ratios REE/Al and P/Al were found to be well-suited to estimate the influence of P-fertiliser on REE content.
Conclusions
This paper points out the need for detailed studies of the geochemical composition of REE in fluvial sediments and careful consideration of the influence of hydrodynamic sorting and anthropogenic activity when REE geochemistry is used as a provenance tool.
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References
Alfaro MR, Nascimento CWA, Biondi CM, Silva YJAB, Silva YJAB, Accioly AMA, Montero A, Ugarte OM, Estevez J (2018) Rare earth-element geochemistry in soils developed in different geological settings of Cuba. CATENA 162:317–324
Allison LE, Moodie CD (1965) Carbonate. In: Black CA (ed), Methods of soil analysis, part 2, second ed., pp. 1379–1400 Agronomy Monography 9 ASA, CSSA and SSSA
Aubert D, Stille P, Probst A (2001) REE fractionation during granite weathering and removal by waters and suspended loads: Sr and Nd isotopic evidence. Geochim Cosmochim Acta 65(3):387–406
Babić-Mladenović M, Bekić D, Grošelj S, Kupusović T, Mikoš M, Oskoruš D, Damjanović V, Ninković D, Milačič M, Petković S (2013) Towards practical guidance for sustainable sediment management using the Sava River Basin as a showcase. ISRBC-International Sava River Basin Commission, Zagreb, Croatia, 1–87
Bayon G, Douglas GB, De Deckker P, Monin L (2020) Preferential riverine export of fine volcanogenic particles to the southeast Australian margin. Front Mar Sci 7:89. https://doi.org/10.3389/fmars.2020.00089
Bayon G, Toucanne S, Skonieczny C, André L, Bermell S, Cheron S, Dennielou B, Etoubleau J, Freslon N, Gauchery T, Germain Y, Jorry SJ, Menot G, Monin L, Ponzevera E, Rouget ML, Tachikawa K, Barrat JA (2015) Rare earth elements and neodymium isotopes in world river sediments revisited. Geochim Cosmochim Acta 170:17–38
Bouchez J, Gaillardet J, France-Lanord C, Maurice L, Dutra-Maia P (2011) Grain size control of river suspended sediment geochemistry: clues from Amazon River depth profiles. Geochem Geophy Geosy 12(3). https://doi.org/10.1029/2010gc003380
Brito P, Prego R, Mil-Homens M, Caçador I, Caetano M (2018) Sources and distribution of yttrium and rare earth elements in surface sediments from Tagus estuary, Portugal. Sci Total Environ 621:317–325
Dinis P, Garzanti E, Hahn A, Vermeesch P, Pinto MC (2019) Weathering indices as climate proxies. A step forward based on Congo and SW African river muds. Earth Sci Rev 103039
Dinis P, Garzanti E, Vermeesch P, Huvi J (2017) Climatic zonation and weathering control on sediment composition (Angola). Chem Geol 467:110–121
Dolenec T, Serafimovski T, Tasev G, Dobnikar M, Dolenec M, Rogan N (2007) Major and trace elements in paddy soil contaminated by Pb–Zn mining: a case study of Kočani Field, Macedonia. Environ Geochem Health 29:21–32
Drolc A, Zagorc-Koncan J, Tisler T (2007) Evaluation of point and diffuse sources of nutrients in a river basin on base of monitoring data. Environ Monit Assess 129(1–3):461–470
Fiket Ž, Mikac N, Kniewald G (2017a) Influence of the geological setting on the REE geochemistry of estuarine sediments: a case study of the Zrmanja River estuary (eastern Adriatic coast). J Geochem Explor 182:70–79
Fiket Ž, Mikac N, Kniewald G (2017b) Mass fractions of forty-six major and trace elements, including rare earth elements, in sediment and soil reference materials used in environmental studies. Geostand Geoanalytical Res 41(1):123–135
Fralick PW, Kronberg BI (1997) Geochemical discrimination of clastic sedimentary rock sources. Sediment Geol 113:111–124
Frančišković-Bilinski S (2008) Detection of geochemical anomalies in stream sediments of the upper Sava River drainage basin (Slovenia, Croatia). Fresenius Environ Bull 17:188–196
Garzanti E, Andó S, France-Lanord C, Censi P, Vignola P, Galy V, Lupker M (2011) Mineralogical and chemical variability of fluvial sediments 2. Suspended-load silt (Ganga–Brahmaputra, Bangladesh). Earth Planet Sci Lett 302(1–2):107–120
Garzanti E, Padoan M, Ando S, Resentini A, Vezzoli G, Lustrino M (2013) Weathering and relative durability of detrital minerals in equatorial climate: sand petrology and geochemistry in the East African Rift. J Geol 121(6):547–580
Gosar M, Šajn R, Bavec S, Gaberšek M, Pezdir V, Miler M (2019) Geochemical background and threshold for 47 chemical elements in Slovenian topsoil. Geologija 62(1):5–57
Guo Y, Yang S, Su N, Li C, Yin P, Wang Z (2018) Revisiting the effects of hydrodynamic sorting and sedimentary recycling on chemical weathering indices. Geochim Cosmochim Acta 227:48–63
Hannigan RE, Sholkovitz ER (2001) The development of middle rare earth element enrichments in freshwaters: weathering of phosphate minerals. Chem Geol 175(3–4):495–508
He M, Zheng H, Clift PD, Tada R, Wu W, Luo C (2015) Geochemistry of fine-grained sediments in the Yangtze River and the implications for provenance and chemical weathering in East Asia. Prog Earth Planet Sci 2(1)
Hillier S (2003) Quantitative analysis of clay and other minerals in sandstones by X-ray powder diffraction (XRPD). Clay mineral cements in sandstones. Int Assoc Sedimentol Spec Publ 34:213–251
Hudson-Edwards KA, Macklin MG, Brewer PA, Dennis IA (2008) Assessment of metal mining-contaminated river sediments in England and Wales (Science Report SC030136/4). Bristol: Environment Agency
Jurković I (2005) Magnetite-hematite iron ore occurrences in the Triassic-Paleozoic metamorphic complex of Medvednica, Croatia. Rudarsko-Geološko-Naftni Zbornik 17:1–14
Kaegi R, Gogos A, Voegelin A, Hug SJ, Winkel LHE, Buser AM, Berg M (2021) Quantification of individual Rare Earth Elements from industrial sources in sewage sludge. Water Res X 11: 100092
Kalender L, Aytimur G (2016) REE geochemistry of Euphrates River. Turkey J Chem 2016:1–13
Kawasaki A, Kimura R, Arai S (1998) Rare earth elements and other trace elements in wastewater treatment sludges. Soil Sci Plant Nutr 44:433–441
Komar PD (2007) The entrainment, transport and sorting of heavy minerals by waves and currents. In: Mange MA, Wright DT (ed) Heavy Minerals in Use. Dev Sedimentol 58:3–48
Kulaksız S, Bau M (2013) Anthropogenic dissolved and colloid/nanoparticle-bound samarium, lanthanum and gadolinium in the Rhine River and the impending destruction of the natural rare earth element distribution in rivers. Earth Planet Sci Lett 362:43–50
Laceby JP, Evrard O, Smith HG, Blake WH, Olley JM, Minella JPG, Owens PN (2017) The challenges and opportunities of addressing particle size effects in sediment source fingerprinting: A review. Earth Sci Rev 169:85–103
Li CS, Shi XF, Kao SJ, Liu YG, Lyu HH, Zou JJ, Liu SF, Qiao SQ (2013) Rare earth elements in fine-grained sediments of major rivers from the high-standing island of Taiwan. J Asian Earth Sci 69:39–47
Lučić M, Mikac N, Bačić N, Vdović N (2020) Appraisal of geochemical composition and hydrodynamic sorting of the river suspended material: application of time-integrated suspended sediment sampler in a medium-sized river (the Sava River catchment). J Hydrol. https://doi.org/10.1016/j.jhydrol.2020.125768
McLennan SM (1989) Rare earth elements in sedimentary rocks: influence of provenance and sedimentary processes. In: Lipin BR, McKay GA, (ed) Geochemistry and mineralogy of rare earth elements. Reviews in Mineralogy, vol 21. Mineral Soc Am. Washington, DC, pp 169–200
Milačič R, Zuliani T, Vidmar J, Oprčkal P, Ščančar J (2017) Potentially toxic elements in water and sediments of the Sava River under extreme flow events. Sci Total Environ 605–606:894–905
Möller P, Knappe A, Dulski P (2014) Seasonal variations of rare earths and yttrium distribution in the lowland Havel River, Germany, by agricultural fertilization and effluents of sewage treatment plants. Appl Geochem 41:62–72
Ogorelec B, Bole B, Leonidakis J, Cermelj B, Mišič M, Faganeli J (2006) Recent sediment of Lake Bled (NW Slovenia): sedimentological and geochemical properties. Water Air Soil Pollut 6(5–6):505–513
Otero N, Vitòria L, Soler A, Canals A (2005) Fertiliser characterisation: major, trace and rare earth elements. Appl Geochem 20(8):1473–1488
Pavlović P, Marković M, Kostić O, Sakan S, Đorđević D, Perović V, Pavlović D, Pavlović M, Čakmak D, Jarić S, Paunović M, Mitrović M (2019) Evaluation of potentially toxic element contamination in the riparian zone of the River Sava. CATENA 174:399–412
Pérez-López R, Macías F, Cánovas CR, Sarmiento AM, Pérez-Moreno SM (2016) Pollutant flows from a phosphogypsum disposal area to an estuarine environment: an insight from geochemical signatures. Sci Total Environ 553:42–51
Placer L (2008) Principles of the tectonic subdivision of Slovenia. Geologija 51(2):205–217
R core team (2017) R: a language and environment for statistical computing. R Foundation for statistical computing, Vienna, Austria. http://www.R-project.org
Ribčič M, Šinigoj J, Komac M (2003) New general engineering geological map of Slovenia. Geologija 46(2):397–404
Rismal M, Kompare B, Rajar R (1997) Contribution of hydrodynamic and limnological modelling to the sanitation of Lake Bled. WIT Trans Ecol Environ 20:125–139
Salehi M, Beni OH, Harchegani HB, Borujeni IE, Motaghian H (2011) Refining soil organic matter determination by loss-on-ignition. Pedosphere 21:473–482
Singh P (2009) Major, trace and REE geochemistry of the Ganga River sediments: influence of provenance and sedimentary processes. Chem Geol 266(3–4):242–255
Singh P, Rajamani V (2001) REE geochemistry of recent clastic sediments from the Kaveri floodplains, southern India: implication to source area weathering and sedimentary processes. Geochim Cosmochim Acta 65(18):3093–3108
Su N, Yang S, Guo Y, Yue W, Wang X, Yin P, Huang X (2017) Revisit of rare earth element fractionation during chemical weathering and river sediment transport. Geochem Geophy Geosy 18(3):935–955
Ščančar J, Heath E, Zuliani T, Horvat M, Kotnik J, Perko P, Milačič R (2015) Elements and persistent organic pollutants in the sediments of the river Sava. In: Milačič R, Ščančar J, Paunović M (ed) Handbook of Environmental Chemistry. Barceló D, Kostianoy AG (ed) The River Sava. Springer, Dordrecht, Heidelberg, New York, London, pp 95–123
Tang J, Johannesson KH (2010) Rare earth elements adsorption onto Carrizo sand: influence of strong solution complexation. Chem Geol 279(3–4):120–133
Taylor SR, McLennan SM (1985) The continental crust: its composition and evolution. An examination of the geochemical record preserved in sedimentary rocks. Blackwell Scientific Publications, Oxford
Tostevin R, Shields GA, Tarbuck GM, He T, Clarkson MO, Wood RA (2016) Effective use of cerium anomalies as a redox proxy in carbonate-dominated marine settings. Chem Geol 438:146–162
Tošić I, Zorn M, Ortar J, Unkašević M, Gavrilov MB, Marković S (2016) Annual and seasonal variability of precipitation and temperatures in Slovenia from 1961 to 2011. Atmos Res 168:220–233
Vermeesch P (2019) Exploratory analysis of provenance data using R and the provenance package. Minerals 9(3):193. https://doi.org/10.3390/min9030193
Vermeesch P, Garzanti E (2015) Making geological sense of ‘Big Data’ in sedimentary provenance analysis. Chem Geol 409:20–27
Vidmar J, Zuliani T, Novak P, Drinčić A, Ščančar J, Milačič R (2017) Elements in water, suspended particulate matter and sediments of the Sava River. J Soils Sediments 17:1917–1927
Vivian C (1986) Rare-earth element content of sewage sludges dumped at sea in Liverpool Bay, UK. Environ Technol Lett 7:593–596
Xu Z, Lim D, Choi J, Yang S, Jung H (2009) Rare earth elements in bottom sediments of major rivers around the Yellow Sea: implications for sediment provenance. Geo-Mar Lett 29(5):291–300
Yoshida S, Muramatsu Y, Tagami K, Uchida S (1998) Concentrations of lanthanide elements Th, and U in 77 Japanese surface soils. Environ Int 24(3):375–386
Zhang KJ, Li QH, Yan LL, Zeng L, Lu L, Zhang YX, Hui J, Jin X, Tang XC (2017) Geochemistry of limestones deposited in various plate tectonic settings. Earth Sci Rev 167:27–46
Zorn M, Ferk M, Lipar M, Komac B, Tičar J, Hrvatin M (2020) Landforms of Slovenia. In: Perko D, Ciglič R, Zorn M (ed) The geography of Slovenia. World Regional Geography Book Series. Springer, Cham, pp 35–57
Acknowledgements
We are deeply thankful to four anonymous reviewers for their useful comments and constructive criticism, and to JSS Editor-in-Chief Philip N. Owens and Submissions Editor Simon Pulley for their suggestions and careful editing of the manuscript. We are also indebted to Željka Fiket for valuable help in the preparation of the manuscript.
Funding
This work has been supported by the Croatian Science Foundation under the project 7555 (TRACESS) and Ministries of Sciences and Education of Republic of Croatia and Slovenia under the bilateral Croatian–Slovenian project.
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Lučić, M., Vdović, N., Bačić, N. et al. Disentangling the influence of lithology and non-provenance factors on the geochemistry of rare earth elements: a study of fine-grained sediments from the Sava River headwaters (Slovenia, Croatia). J Soils Sediments 21, 3704–3716 (2021). https://doi.org/10.1007/s11368-021-03039-1
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DOI: https://doi.org/10.1007/s11368-021-03039-1