Skip to main content
Log in

Prioritisation of organic contaminants in a river basin using chemical analyses and bioassays

  • Research Article
  • Published:
Environmental Science and Pollution Research Aims and scope Submit manuscript

Abstract

Region-specific contaminant prioritisation is an important prerequisite for sustainable and cost-effective monitoring due to the high number of different contaminants that may be present. Surface water and sediment samples from the Sava River, Croatia, were collected at four locations covering a 150-km-long river section characterised by well-defined pollution gradients. Analysis of contaminant profiles along the pollution gradients was performed by combining toxicity screening using a battery of small-scale or in vitro bioassays, which covered different modes of action, with detailed chemical characterisation based on gas chromatography/mass spectrometry (GC/MS) and liquid chromatography/quadrupole time-of-flight mass spectrometry (LC-QTOF-MS). A large number of contaminants, belonging to different toxicant classes, were identified in both analysed matrices. Analyses of water samples showed that contaminants having polar character occurred in the highest concentrations, while in sediments, contributions from both non-polar and amphiphilic contaminants should be taken into account. Estimated contributions of individual contaminant classes to the overall toxicity indicated that, besides the classical pollutants, a number of emerging contaminants, including surfactants, pharmaceuticals, personal care products and plasticizers, should be taken into consideration in future monitoring activities. This work demonstrates the importance of the integrated chemical and bioanalytical approach for a systematic region-specific pollutant prioritisation. Finally, the results presented in this study confirm that hazard assessment in complex environmental matrices should be directed towards identification of key pollutants, rather than focusing on a priori selected contaminants alone.

This is a preview of subscription content, log in via an institution to check access.

Access this article

Price excludes VAT (USA)
Tax calculation will be finalised during checkout.

Instant access to the full article PDF.

Fig. 1
Fig. 2
Fig. 3
Fig. 4
Fig. 5

Similar content being viewed by others

References

  • Aerni HR, Kobler B, Rutishauser BV, Wettstein FE, Fischer R, Giger W, Hungerbuhler A, Marazuela MD, Peter A, Schonenberger R, Vogeli AC, Suter MJ, Eggen IR (2004) Combined biological and chemical assessment of estrogenic activities in wastewater treatment plant effluents. Anal Bioanal Chem 378:688–696

    Article  CAS  Google Scholar 

  • Ahel M (1991) Infiltration of organic pollutants into groundwater: field studies in the alluvial aquifer of the Sava River. Bull Environ Contam Toxicol 47:586–593

    Article  CAS  Google Scholar 

  • Biselli S, Reineke N, Heinzel N, Kammann U, Franke S, Huehnerfuss H, Theobald NJ (2005) Bioassay-directed fractionation of organic extracts of marine surface sediments from the North and Baltic Sea — Part I: Determination and identification of organic pollutants. J Soils Sed 5:171–181

    Article  CAS  Google Scholar 

  • Blasco C, Pico Y (2009) Prospects for combining chemical and biological methods for integrated environmental assessment. Trends Anal Chem 28:745–757

    Article  CAS  Google Scholar 

  • Brack W (2003) Effect–directed analysis: a promising tool for the identification of organic toxicants in complex mixtures. Anal Bioanal Chem 377:397–407

    Article  CAS  Google Scholar 

  • Brack W, Klamer HJC, De Alda ML, Barceló D (2007) Effect-directed analysis of key toxicants in European river basins: a review. Environ Sci Pollut R 14:30–38

    Article  CAS  Google Scholar 

  • Brack WH, Segner M, Moder M, Schuurmann G (2000) Fixed-effect-level toxicity equivalents - A suitable parameter for assessing ethoxyresorufin-O-deethylase induction potency in complex environmental samples. Environ Toxicol Chem 19:2491–2501

    Google Scholar 

  • Dierickx PJ (1999) Glutathione-dependent cytotoxicity of the chloroacetanilide herbicides alachlor, metolachlor, and propachlor in rat and human hepatoma-derived cultured cells. Cell Biol Toxicol 15:325–332

    Article  CAS  Google Scholar 

  • Dragun Z, Raspor B, Roje V (2008) The labile metal concentrations in Sava River water assessed by diffusive gradients in thin films. Chem Spec Bioavail 20:33–46

    Article  CAS  Google Scholar 

  • EU WFD (2000) Directive 2000/60/EC of the European Parliament and of the Council of 23 October 2000 establishing a framework for Community action in the field of water policy. Available at: http://eur-lex.europa.eu/LexUriServ/LexUriServ.do?uri=CELEX:32000L0060:EN:NOT

  • Goetz CW, Stamm C, Fenner K, Singer H, Scharer M, Hollender J (2010) Targeting aquatic microcontaminants for monitoring: exposure categorization and application to the Swiss situation. Environ Sci Pollut 17:341–354

    Article  Google Scholar 

  • Grung M, Lichtenthaler R, Ahel M, Tollefsen KE, Langford K, Thomas KV (2007) Effects-directed analysis of organic toxicants in wastewater effluent from Zagreb, Croatia. Chemosphere 67:108–120

    Article  CAS  Google Scholar 

  • Harris CA, Henttu P, Parker MG, Sumpter JP (1997) The estrogenic activity of phthalate esters in vitro. Environ Health Perspect 105:802–811

    Article  CAS  Google Scholar 

  • Harris CA, Brian JV, Pojana G, Lamoree M, Booy P, Marcomini A, Sumpter JP (2009) The influence of a surfactant, linear alkylbenzene sulfonate, on the estrogenic response to a mixture of (xeno)estrogens in vitro and in vivo. Aquat Toxicol 91:95–98

    Article  CAS  Google Scholar 

  • Hellenius A, Simons K (1975) Solubilization of membranes by detergents. Biochim Biophys Acta 415:29–79

    Article  Google Scholar 

  • Hirose T, Morito K, Kizu R, Toriba A, Hayakawa K, Ogawa S, Inoue S, Muramatsu M, Masamune Y (2001) Estrogenic/antiestrogenic activities of benzo[a]pyrene monohydroxy derivatives. J Health Sci 47:552–558

    Article  CAS  Google Scholar 

  • Kallqvist T, Milacic R, Smital T, Thomas KV, Vranes S, Tollefsen KE (2008) Chronic toxicity of the Sava River (SE Europe) sediments and river water to the algae Pseudokirchneriella subcapitata. Water Res 42:2146–2156

    Article  Google Scholar 

  • Kastelan-Macan M, Ahel M, Horvat AJM, Jabucar D, Jovancic P (2007) Water resources and waste water management in Bosnia and Herzegovina, Croatia and the State Union of Serbia and Montenegro. Water Policy 9:319–343

    Article  Google Scholar 

  • Kile DE, Chiou CT (1989) Water solubility enhancement of DDT and trichlorobenzene by some surfactants below and above the critical micelle concentration. Environ Sci Technol 23:832–838

    Article  CAS  Google Scholar 

  • Kolpin DW, Furlong ET, Meyer MT, Thurman EM, Zaugg SD, Barber LB, Buxton HT (2002) Pharmaceuticals, hormones, and other organic wastewater contaminants in U.S. streams, 1999–2000: a national Rrconnaissance. Environ Sci Technol 36:1202–1211

    Article  CAS  Google Scholar 

  • Krca S, Zaja R, Calic V, Terzic S, Grubesic MS, Ahel M, Smital T (2007) Hepatic biomarker responses to organic contaminants in feral chub (Leuciscus cephalus) – laboratory characterization and field study in the Sava River, Croatia. Environ Toxicol Chem 26:2620–2633

    Article  CAS  Google Scholar 

  • Kunz PY, Galicia HF, Fent K (2006) Comparison of in vitro and in vivo estrogenic activity of UV filters in fish. Toxicol Sci 90:349–361

    Article  CAS  Google Scholar 

  • Labadie P, Hill EM (2007) Analysis of estrogens in river sediments by liquid chromatography-electrospray ionisation mass spectrometry — comparison of tandem mass spectrometry and time-of-flight mass spectrometry. J Chromatogr A 1141:174–181

    Article  CAS  Google Scholar 

  • Laville N, Ait-Aissa S, Gomez E, Casellas C, Porcher JM (2004) Effects of human pharmaceuticals on cytotoxicity, EROD activity and ROS production in fish hepatocytes. Toxicology 196:41–55

    Article  CAS  Google Scholar 

  • Radic S, Stipanicev D, Vujcic V, Rajcic MM, Sirac S, Pevalek-Kozlina B (2010) The evaluation of surface and wastewater genotoxicity using the Allium cepa test. Sci Total Environ 408:1228–1233

    Article  CAS  Google Scholar 

  • Reemtsma T, Weiss S, Mueller J, Petrovic M, Gonzalez S, Barcelo D, Ventura F, Knepper TP (2006) Polar pollutants entry into the water cycle by municipal wastewater: a European perspective. Environ Sci Technol 40:5451–5458

    Article  CAS  Google Scholar 

  • Schwarzenbach RP, Escher B, Fenner K, Hofstetter TB, Johnson CA, von Gunten U, Wehrli B (2006) The challenge of micropollutants in aquatic systems. Science 313:1072–1077

    Article  CAS  Google Scholar 

  • Seelig A, Gatlik-Landwojtowicz E (2005) Inhibitors of multidrug efflux transporters: their membrane and protein interactions. Mini Rev Med Chem 5:135–151

    Article  CAS  Google Scholar 

  • Senta I (2009) Occurrence and behaviour of sulfonamides, fluoroquinolones, macrolides and trimethoprim in wastewater and natural waters. PhD thesis, University of Zagreb, 120pp

  • Senta I, Terzic S, Ahel M (2008) Simultaneous determination of sulfonamides, fluoroquinolones, macrolides and trimethoprim in wastewater and river water by LC-tandem-MS. Chromatographia 68:747–758

    Article  CAS  Google Scholar 

  • Smital T, Terzic S, Zaja R, Senta I, Pivcevic B, Popovic M, Mikac I, Tollefsen KE, Thomas KV, Ahel M (2011) Assessment of toxicological profiles of the municipal wastewater effluents using chemical methods and bioassays. Ecotoxicol Environ Saf 74:844–851

    Article  CAS  Google Scholar 

  • Tabor CF, Barber LB (1996) Fate of linear alkylbenzene sulfonate in the Mississippi River. Environ Sci Technol 30:161–171

    Article  CAS  Google Scholar 

  • Terzic S, Ahel M (2011) Nontarget analysis of polar contaminants in freshwater sediments influenced by pharmaceutical industry using ultra-high-pressure liquid chromatography – quadrupole time-of-flight mass spectrometry. Environ Pollut 159:557–566

    Article  CAS  Google Scholar 

  • Terzic S, Matosic M, Ahel M, Mijatovic I (2005) Elimination of aromatic surfactants from municipal wastewaters – comparison of conventional activated sludge treatment and membrane biological reactor. Water Sci Technol 51:447–453

    CAS  Google Scholar 

  • Terzic S, Senta I, Ahel M, Gros M, Petrovic M, Barcelo D, Müller J, Knepper TP, Martí I, Ventura F, Jovancic P, Jabucar D (2008) Occurrence and fate of emerging wastewater contaminants in Western Balkan Region. Sci Total Environ 399:66–77

    Article  CAS  Google Scholar 

  • Terzic S, Mikac I, Senta I, Ahel M (2009) Comprehensive molecular characterization of organic contaminants in freshwater sediments by gas chromatography/mass spectrometry and liquid chromatography/time-of-flight mass spectrometry. In: Li S, Wang Y, Cao F, Huang P, Zhang Y (eds) Progress in environmental science and technology, vol II, Part A. Science Press, Beijing, pp 397–405

    Google Scholar 

  • Thomas KV, Hurst MR, Matthiessen P, Waldock MJ (2001) Characterization of estrogenic compounds in water samples collected from United Kingdom estuaries. Environ Toxicol Chem 20:2165–2170

    Article  CAS  Google Scholar 

  • Thomas KV, Balaam J, Lavender J, Jones C (2002) Characterisation of potentially genotoxic compounds in sediments collected from United Kingdom estuaries. Chemosphere 49:247–258

    Article  CAS  Google Scholar 

  • Tollefsen KE (2007) Binding of alkylphenols and alkylated non-phenolics to the rainbow trout (Oncorhynchus mykiss) plasma sex steroid-binding protein. Ecotox Environ Saf 68:40–48

    Article  CAS  Google Scholar 

  • Tollefsen KE, Eikvar S, Finne EF, Fogelberg O, Gregersen IK (2008) Estrogenicity of alkylphenols and alkylated non-phenolics in a rainbow trout (Oncorhynchus mykiss) primary hepatocyte culture. Ecotoxicol Environ Saf 71:370–383

    Article  CAS  Google Scholar 

  • Tremblay L, Van der Kraak G (1998) Use of a series of homologous in vitro and in vivo assays to evaluate the endocrine modulating actions of β-sitosterol in rainbow trout. Aquat Toxicol 43:149–162

    Article  CAS  Google Scholar 

  • van Lipzig MMH, Vermeulen NPE, Gusinu R, Legler J, Frank H, Seidel A, Meerman JHN (2005) Formation of estrogenic metabolites of benzo[a]pyrene and chrysene by cytochrome P450 activity and their combined and supra-maximal estrogenic activity. Environ Toxicol Pharmacol 19:41–55

    Article  Google Scholar 

  • von der Ohe PC, Dulio V, Slobodnik J, De Deckere E, Kuhne R, Ebert RU, Ginebreda A, De Cooman W, Schuurmann G, Brack W (2011) A new risk assessment approach for the prioritization of 500 classical and emerging microcontaminants as potential river basin specific pollutants under the European Water Framework Directive. Sci Total Environ 409:2064–2077

    Article  Google Scholar 

  • Wang L, Ying GG, Chen F, Zhang LJ, Zhao JL, Lai HJ, Chen ZF, Tao R (2012) Monitoring of selected estrogenic compounds and estrogenic activity in surface water and sediment of the Yellow River in China using combined chemical and biological tools. Environ Pollut 165:241–249

    Article  CAS  Google Scholar 

  • Wei C, Caccavale RJ, Weyand EH, Chen S, Iba MM (2002) Induction of CYP1A1 and CYP1A2 expressions by prototypic and atypical inducers in the human lung. Cancer Lett 178:25–36

    Article  CAS  Google Scholar 

  • Ying GG (2006) Fate, behavior and effects of surfactants and their degradation products in the environment. Environ Int 32:417–431

    Article  CAS  Google Scholar 

Download references

Acknowledgements

The work presented here has been supported through the NATO Science for Peace and Security Program, Project SfP 982590 – “Assessment of hazardous chemical contamination in the Sava River basin” (http://www.irb.hr/nato-savariver/). In addition, this work was partially supported by the Ministry of Science, Education and Sports of the Republic of Croatia, Project Nos: 098-0982934-2745 and 098-0982934-2712 and with institutional funding from the Norwegian Institute for water Research (NIVA). We thank Nenad Muhin for the technical assistance.

Author information

Authors and Affiliations

Authors

Corresponding author

Correspondence to Marijan Ahel.

Additional information

Responsible editor: Philippe Garrigues

Electronic supplementary material

Below is the link to the electronic supplementary material.

ESM 1

(DOC 195 kb)

Rights and permissions

Reprints and permissions

About this article

Cite this article

Smital, T., Terzić, S., Lončar, J. et al. Prioritisation of organic contaminants in a river basin using chemical analyses and bioassays. Environ Sci Pollut Res 20, 1384–1395 (2013). https://doi.org/10.1007/s11356-012-1059-x

Download citation

  • Received:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1007/s11356-012-1059-x

Keywords

Navigation