Abstract
The objective of this paper was to determine background values (BV) and anomalous values (AV) of U and Th in groundwater and to establish hydrogeochemical conditions which lead to the elevated concentrations of these elements in groundwater. The methodology included planning and collecting of water samples, laboratory work, and assessment of BV and AV concentrations in accordance with the dataset distribution, based on consideration of hydrogeochemical conditions in the hydrogeological system. Groundwater sampling included 144 occurrences of mineral and thermal water from Serbian territory, belonging to different hydrogeological systems. Field parameters were measured for temperature (T), pH, electrical conductivity (EC), oxidation–reduction potential (ORP), dissolved oxygen (DO), and carbon dioxide (CO2). Standard laboratory measurements were applied for the determination of major chemical components (Ca, Mg, Na, K, Cl, HCO3, and SO4) and U and Th concentrations were measured by ICP-MS. The first step for obtaining U and Th threshold values was based on non-parametric statistical analysis on the data sets. Further analysis of threshold values enabled establishing hydrogeochemical conditions influencing elevated concentrations of U and Th and setting up the logistic regression (LR) model. Differences in the hydrochemical properties of U and Th can be observed based on predictor variables from LR models. Physico-chemical parameters Eh and pH, groundwater type, and geochemical environment (cretaceous igneous rocks) were significant predictors for elevated uranium concentrations, while significant predictors in the thorium LR model were the pH value, the concentration of SO4 in the solution, and the water-bearing rocks (tertiary igneous rocks).
Similar content being viewed by others
References
Allard B, Olofsson U, Torstenfelt B, Kipasti H, Andersson K (1982) Sorption of actinides in well-defined oxidation states on geologic media. Mater Res Soc Symp Proc 11:775–782
Ander EL, Johnson CC, Cave MR, Palumbo-Roe B, Nathanail P, Lark RM (2013) Methodology for the determination of normal background concentrations of contaminants in English soil. Sci Total Environ 454:604–618
Antweiler RC, Taylor HE (2008) Evaluation of statistical treatments of left-censored environmental data using coincident uncensored data sets: I. Summary statistics. Environ Sci Technol 42(10):3732–3738
Appelo CAJ, Postma D (1999) Geochemistry, groundwater and pollution. AA Balkema, Rotterdam
Bendel RB, Afifi AA (1977) Comparison of stopping rules in forward regression. J Am Stat Assoc 72:46–53. https://doi.org/10.2307/2286904
Bewick V, Cheek L, Ball J (2005) Statistics review 14: logistic regression. Crit Care 9(1):112–118
Chow C, Andrášik R, Fischer B, Keiler M (2019) Application of statistical techniques to proportional loss data: evaluating the predictive accuracy of physical vulnerability to hazardous hydro-meteorological events. J Environ Manag 246:85–100. https://doi.org/10.1016/j.jenvman.2019.05.084
Cox DR (1958) The regression analysis of binary sequences (with discussion). J R Stat Soc B 20:215–242
Cvetković V, Koroneos A, Christofides G, Poli G, Knežević V, Erić V (2002) Granitoids of Mt. Cer and Mt. Bukulja and their significance for geodynamics of The Southern Pannonian Realm. In: Extended Abstract volume, XVII Congress of CBGA, Bratislava, pp 1–4
Cvetković V, Prelević D, Downes H, Jovanović M, Vaselli O, Pecskay Z (2004) Origin and geodynamic significance of tertiary postcollisional basaltic magmatism in Serbia (central Balkan Peninsula). Lithos 73:161–186
Cvetković V, Poli G, Christofides G et al (2007) The Miocene granitoid rocks of Mt. Bukulja (central Serbia): evidence for Pannonian extension-related granitoid magmatsim in the northern Dinarides. Eur J Mineral 19(4):513–532
Cvetković V, Prelević D, Schmid S (2016) Geology of South-Eastern Europe. In: Papić P (ed) Mineral and thermal waters of Southeastern Europe. Springer International Publishing, Cham, pp 1–29
Dementyev VS, Syromyatnikov NG (1968) Conditions of formation of a sorption barrier to the migration of uranium in an oxidizing environment. Geochem Int 5:394–400
Dragović S, Janković-Mandić LJ, Dragović R, Kovačević J (2014) Lithogenic radionuclides in surface soils of Serbia: spatial distribution and relation to geological formations. J Geochem Explor 142:4–10
EPA/600/R-07/041 ProUCL Version 5.1 User Guide Statistical Software for Environmental Applications for Data Sets with and without Nondetect Observations. Prepared by: Singh A, Maichle R, Martin L/SERAS IS&GS-CIVIL 2890 Woodbridge Ave Edison NJ 08837. U.S. Environmental Protection Agency Office of Research and Development Washington, DC 20460
European Food Safety Authority (2009) Uranium in foodstuffs, in particular mineral water. Scientific opinion of the panel on contaminants in the food chain. EFSA J 1018:1–59
Fan J, Upadhye S, Worster A (2006) Understanding receiver operating characteristic (ROC) curves. CJEM 8(1):19–20
Faraggi D, Reiser B (2002) Estimation of the area under the ROC curve. Stat Med 21(20):3093–3106
Fawcett T (2006) An introduction to ROC analysis. Pattern Recogn Lett 27(8):861–874. https://doi.org/10.1016/j.patrec.2005.10.010
Fiket Ž, Rožmarić M, Krmpotić M, Petrinec B (2015) Trace and rare earth element geochemistry of Croatian thermal waters. Int J Environ Res 9(2):595–604
Filipović B (2003) Mineral, thermal and thermo-mineral water of Serbia. University of Belgrade, Faculty of Mining and Geology (in Serbian)
Finch R, Murakami T (1999) Systematics and paragenesis of uranium minerals. Rev Mineral 38:91–180
Fox P, Davis J, Zachara J (2006) The effect of calcium on aqueous uranium(VI) speciation and adsorption to ferrihydrite and quartz. Geochim Cosmochim Acta 70:1379–1387
Greene EA, LaMotte AE, Cullinan KA, Smith ER (2004) Groundwater vulnerability to nitrate contamination in the Mid-Atlantic region. USGS, Baltimore
Helsel D, Cohn T (1988) Estimation of descriptive statistics for multiply censored water quality data. Water Resour Res 24(12):1997–2004
Helsel DR, Hirsch RM (1992) Statistical methods in water resources. Elsevier, Amsterdam (ISBN 0-444-81463-9)
Helsel DR, Hirsch RM (2002) Statistical methods in water resources. Techniques of water resources investigations of the United States Geological Survey. Hydrologic analysis and interpretation. USGS, Reston
Klein JR, Roodman A (2005) Blind analysis in nuclear and particle physics. Annu Rev Nucl Part Sci 55:141–163
Kopylova Y, Guseva N, Shestakova A, Khvaschevskaya A, Arakchaa K (2015) Uranium and thorium behavior in groundwater of the natural spa area Choygan mineral water (East Tuva). IOP Conference Series. Earth Environ Sci 27:1–6
Koroneos A, Poli G, Cvetković V, Christofides D, Krstić D, Pécskay Z (2010) Petrogenetic and tectonic inferences from the study of the Mt Cer pluton (West Serbia). Geol Mag 148(1):89–111
Langmuir D (1997) Aqueous environmental geochemistry. Prentice Hall. Inc, Upper Saddle River
Li J (2017) Assessing the accuracy of predictive models for numerical data: Not r nor r2, why not? Then what? PLoS ONE 12(8):e0183250. https://doi.org/10.1371/journal.pone.0183250
MacCoun R, Perlmutter S (2015) Hide results to seek the truth. Nature 526:187–189
Matschullat J, Ottenstein R, Reimann C (2000) Geochemical background—can we calculate it? Environ Geol 39:990–1000
Mernagh PT, Miezitis Y (2008) A review of the geochemical processes controlling the distribution of thorium in the Earth’s crust and Australia’s Thorium Resources. In: Geoscience Australia Record 2008/05
Mladenović A (2015) Stress field evolution in the area of the Internal Dinarides in Serbia during the Alpine orogenic cycle. Dissertation, University of Belgrade, Faculty of Mining and Geology
Molinari A, Guadagnini L, Marcaccio M, Guadagnini A (2012) Natural background levels and threshold values of chemical species in three large-scale groundwater bodies in Northern Italy. Sci Total Environ 425:9–19
Molinari A, Chidichimo F, Straface S, Guadagnin A (2014) Assessment of natural background levels in potentially contaminated coastal aquifers. Sci Total Environ 476(477):38–48
Mouquet N, Lagadeuc Y, Devictor V, Doyen L, Duputie A, Eveillard D et al (2015) Predictive ecology in a changing world. J Appl Ecol 52:1293–1310. https://doi.org/10.1111/1365-2664.12482
Nassef MH, Diab HM (2015) Determination of uranium and thorium concentration in ground water samples by inductively coupled plasma mass spectrometry (ICP-MS) and the associated dose contribution. Int J Environ Sci 4(1):7–13
Nolan BT, Hitt KJ, Ruddy BC (2002) Probability of nitrate contamination of recently recharged groundwaters in the conterminous United States. Environ Sci Technol 36(10):2138–2145
Obuchowski NA, Lieber ML, Wians FH Jr (2004) ROC curves in clinical chemistry: uses, misuses, and possible solutions. Clin Chem 50(7):1118–1125
Paunescu N (1986) Determination of uranium and thorium concentration in natural waters. J Radioanal Nucl Chem 104:209–216
Peng X, Min M, Qian H, Wang J, Fayek M (2015) Uranium-series disequilibria in the groundwater of the Shihongtan sandstone-hosted uranium deposit. NW China Minerals 6(1):1–12
Petković K (1976) Geology of Serbia. VIII—1, Hydrogeology. University of Belgrade. Department of Regional Geology and Paleontology, Faculty of Mining and Geology, Belgrade (In Serbian)
Ravier E, Buoncristiani JF (2018) Glaciohydrogeology. In: J Menzies, van der Meer Jaap JM (eds) Chapter 12. Past glacial environments, 2nd edn. Elsevier, New York, pp 431–466
Reimann C, Garrett RG (2005) Geochemical background—concept and reality. Sci Total Environ 350:12–27
Reiser B, Guttman I (1986) Statistical inference for Pr (Y < X): the normal case. Technometrics 28:253–257
Samaropoulos I, Efstathiou M, Pashalidis I, Ioannidou A (2012) Determination of uranium concentration in ground water samples of Northern Greece. EPJ Web Conf. https://doi.org/10.1051/epjconf/201222403005
Schmid S, Bernoulli D, Fügenschuh B, Matenco L, Schefer S, Schuster R, Tischler M, Ustaszewski K (2008) The Alpine—Carpathian—Dinaride orogenic system: correlation and evolution of tectonic units. Swiss J Geosci 101:139–183
SRPS EN ISO 9963-1:2007. Water quality—Determination of alkalinity—Part 1: Determination of total and composite alkalinity (ISO 9963-1:1994)
Todorović M, Štrbački J, Ćuk M, Andrijašević J, Šišović J, Papić P (2015) Mineral and thermal waters of Serbia: multivariate statistical approach to hydrochemical characterization. In: Papić P (ed) Mineral and thermal waters of Southeastern Europe. Springer International Publishing, Cham, pp 81–95
Toth J (1970) A conceptual model of the groundwater regime and the hydrogeological environment. J Hydrol 10:164–176
Tunkel J, Mayo K, Austin C, Hickerson A, Howard P (2005) Practical considerations on the use of predictive models for regulatory purposes. Environ Sci Technol 39(7):2188–2199. https://doi.org/10.1021/es049220t
Twarakavi NKC, Kaluarachchi JJ (2005) Aquifer vulnerability assessment to heavy metals using ordinal logistic regression. Groundwater 43(2):200–214
USEPA—US Environmental Protection Agency (1999) Integrated Risk Information System (IRIS) on Uranium, Natural. National Center for Environmental Assessment, Office of Research and Development, Washington, DC
Yang Q, Jung HB, Marvinney RG, Culbertson CW, Zheng Y (2012) Can arsenic occurrence rates in bedrock aquifers be predicted? Environ Sci Technol 46(4):2080–2087
Závodská L, Kosorínová E, Ščerbáková L, Lesný J (2008) Environmental chemistry of uranium. HEJ 1–19
Acknowledgements
This work is supported by the Ministry of Education, Science and Technological Development of the Republic of Serbia, within the Project III 43004. The authors would like to thank Vladica Cvetković for reading one of the earlier versions of the manuscript and for useful suggestions to improve the manuscript. Also, the authors owe great gratitude to unknown reviewers who have shown a keen interest in improving this work.
Author information
Authors and Affiliations
Corresponding authors
Additional information
Publisher's Note
Springer Nature remains neutral with regard to jurisdictional claims in published maps and institutional affiliations.
This article is a part of the Topical Collection in Environmental Earth Sciences on “Mineral and Thermal Waters" guest edited by Drs. Adam Porowski, Nina Rman and Istvan Forizs, with James LaMoreaux as the Editor-in-Chief.
Electronic supplementary material
Below is the link to the electronic supplementary material.
Rights and permissions
About this article
Cite this article
Ćuk Đurović, M., Jemcov, I., Todorović, M. et al. Predictive modeling for U and Th concentrations in mineral and thermal waters, Serbia. Environ Earth Sci 79, 456 (2020). https://doi.org/10.1007/s12665-020-09204-y
Received:
Accepted:
Published:
DOI: https://doi.org/10.1007/s12665-020-09204-y