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Assessment of the chemical pollution status of the Dniester River Basin by wide-scope target and suspect screening using mass spectrometric techniques

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Abstract

The quality of the Dniester River Basin has been seriously impacted by the chemicals released by agriculture, industry, and wastewater discharges. To assess its current chemical pollution status, a transboundary monitoring campaign was conducted in May 2019. Thirteen surface water, 13 sediment, and three biota samples were collected and analyzed using generic sample preparation methods for the determination of organic substances by liquid chromatography high-resolution mass spectrometry (LC-HRMS) and metals by inductively coupled plasma mass spectrometry (ICP-MS). Wide-scope target and suspect screening resulted in detection of Water Framework Directive (WFD) priority substances and emerging contaminants, whereas the raw data were stored in NORMAN Digital Sample Freezing Platform (DSFP) for future retrospective screening. Furthermore, risk assessment was performed to prioritize detected substances and propose a draft list of river basin–specific pollutants. All studied metals (As, Hg, Zn, Cu, Cr, Cd, Pb, Ni) were detected in the surface water and sediments. In total, 139 organic contaminants belonging to various chemical classes (pesticides, pharmaceuticals, drugs of abuse, stimulants, sweeteners, industrial chemicals, and their transformation products) were detected. The highest cumulative concentration of contaminants was observed in surface water from the Byk River, a tributary of the Dniester (Moldova). Concentrations of WFD priority substances diuron and mercury and EU Watch List neonicotinoid compounds imidacloprid and thiamethoxam exceeded their environmental quality standards (EQS), whereas concentrations of 23 emerging substances exceeded their predicted no-effect concentration (PNEC) at minimum one site. Emerging contaminants telmisartan, metolachlor, terbuthylazine, and 4-acetamidoantipyrine were prioritized as potential river basin–specific pollutants.

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References

  1. United Nations Economic Commission for Europe. Transboundary diagnostic study for the Dniester River Basin. 2005. (Accessible at https://www.osce.org/ukraine/104057. Last accessed 4 Feb 2020).

  2. Lebedynets M, Sprynskyy M, Kowalkowski T, Buszewski B. Evaluation of hydrosphere state of the Dniester river catchment. Pol J Environ Stud. 2005;14(1):65–71.

    CAS  Google Scholar 

  3. Agreement between the Government of the Republic of Moldova and the Government of Ukraine on the joint management and protection of the cross-border waters. 1994. (Accessible at http://www.cawater-info.net/bk/water_law/pdf/moldova_ukraina_eng.pdf. Last accessed 4 Feb 2020).

  4. Water Code of Ukraine of June 6, 1995 No. 213/95-BP (Accessible at https://zakon.rada.gov.ua/laws/card/ru/213/95-%D0%B2%D1%80?lang=en. Last accessed 4 Feb 2020).

  5. Law of the Republic of Moldova on Water (2011) No. 272 (Accessible at http://www.lawyermoldova.com/2012/10/water-law.html. Last accessed 4 Feb 2020).

  6. Buijs P. Transboundary monitoring of the Dniester River Assessment and evaluation, Action Programme to Improve Transboundary Cooperation and Sustainable Management of the Dniester River Basin (Dniester – III). 2010. (Accessible at http://archive.zoinet.org/web/sites/default/files/publications/transboundary_monitoring_of_the_dniester_river_assessment_and_evaluation-august-2010_0.pdf. Last accessed 4 Feb 2020).

  7. European Commission. 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. Off J Eur Union. 2000;L327:1–72.

    Google Scholar 

  8. Vystavna Y, Cherkashyna M, van der Valk MR. Water laws of Georgia, Moldova and Ukraine: current problems and integration with EU legislation. Water Int. 2018;43(3):424–35. https://doi.org/10.1080/02508060.2018.1447897.

    Article  Google Scholar 

  9. European Commission. DIRECTIVE 2013/39/EU of the European Parliament and of the Council of 12 August 2013 amending Directives 2000/60/EC and 2008/105/EC as regards priority substances in the field of water policy. Off J Eur Union. 2013;L226:1–17.

    Google Scholar 

  10. European Commission (2018) Commission implementing decision (EU) 2018/840 of 5 June 2018 establishing a watch list of substances for Union-wide monitoring in the field of water policy pursuant to Directive 2008/105/EC of the European Parliament and of the Council and repealing Commission Implementing Decision (EU) 2015/495 Official Journal of the European Union L141:9-12.

  11. Dulio V, van Bavel B, Brorstrom-Lunden E, Harmsen J, Hollender J, Schlabach M, et al. Emerging pollutants in the EU: 10 years of NORMAN in support of environmental policies and regulations. Environ Sci Eur. 2018;30(1):5. https://doi.org/10.1186/s12302-018-0135-3.

    Article  PubMed  PubMed Central  Google Scholar 

  12. Beretsou VG, Psoma AK, Gago-Ferrero P, Aalizadeh R, Fenner K, Thomaidis NS. Identification of biotransformation products of citalopram formed in activated sludge. Water Res. 2016;103:205–14. https://doi.org/10.1016/j.watres.2016.07.029.

    Article  CAS  PubMed  Google Scholar 

  13. Nika MC, Bletsou AA, Koumaki E, Noutsopoulos C, Mamais D, Stasinakis AS, et al. Chlorination of benzothiazoles and benzotriazoles and transformation products identification by LC-HR-MS/MS. J Hazard Mater. 2017;323(Pt A):400–13. https://doi.org/10.1016/j.jhazmat.2016.03.035.

    Article  CAS  PubMed  Google Scholar 

  14. Sapozhnikova Y, Zubcov N, Hungerford S, Roy LA, Boicenco N, Zubcov E, et al. Evaluation of pesticides and metals in fish of the Dniester River, Moldova. Chemosphere. 2005;60(2):196–205. https://doi.org/10.1016/j.chemosphere.2004.12.061.

    Article  CAS  PubMed  Google Scholar 

  15. Sapozhnikova Y, Zubcov E, Zubcov N, Schlenk D. Occurrence of pesticides, polychlorinated biphenyls (PCBs), and heavy metals in sediments from the Dniester River, Moldova. Arch Environ Contam Toxicol. 2005;49(4):439–48. https://doi.org/10.1007/s00244-005-8011-8.

    Article  CAS  PubMed  Google Scholar 

  16. Munteanu V, Munteanu G. Biomonitoring of mercury pollution: a case study from the Dniester River. Ecol Indic. 2007;7(2):489–96. https://doi.org/10.1016/j.ecolind.2006.01.002.

    Article  Google Scholar 

  17. Zubcov E, Zubcov N, Ene A, Bagrin N, Biletchi L. The dynamics of trace elements in Dniester river ecosystems. J Sci Art. 2010;2(13):281–6.

    Google Scholar 

  18. Maldonado C, Bayona JM, Bodineau L. Sources, distribution, and water column processes of aliphatic and polycyclic aromatic hydrocarbons in the northwestern Black Sea water. Environ Sci Technol. 1999;33(16):2693–702. https://doi.org/10.1021/es9811647.

    Article  CAS  Google Scholar 

  19. Gago-Ferrero P, Bletsou AA, Damalas DE, Aalizadeh R, Alygizakis NA, Singer HP, et al. Wide-scope target screening of >2000 emerging contaminants in wastewater samples with UPLC-Q-ToF-HRMS/MS and smart evaluation of its performance through the validation of 195 selected representative analytes. J Hazard Mater. 2020;387:121712. https://doi.org/10.1016/j.jhazmat.2019.121712.

    Article  CAS  PubMed  Google Scholar 

  20. Alygizakis NA, Oswald P, Thomaidis NS, Schymanski EL, Aalizadeh R, Schulze T, et al. NORMAN digital sample freezing platform: a European virtual platform to exchange liquid chromatography high resolution-mass spectrometry data and screen suspects in “digitally frozen” environmental samples. TrAC Trends Anal Chem. 2019;115:129–37. https://doi.org/10.1016/j.trac.2019.04.008.

    Article  CAS  Google Scholar 

  21. European Chemicals Bureau. Technical Guidance Document on Risk Assessment in support of Commission Directive 93/67/EEC on Risk Assessment for new notified substances Commission Regulation (EC) No 1488/94 on Risk Assessment for existing substances Directive 98/8/EC of the European Parliament and of the Council concerning the placing of biocidal products on the market. 2003. (Accessible at https://echa.europa.eu/documents/10162/16960216/tgdpart2_2ed_en.pdf. Last accessed 4 Feb 2020).

  22. NORMAN Database System. NORMAN Ecotoxicology Database. 2020. (Accessible at https://www.norman-network.com/nds/ecotox/, Last accessed 4 Feb 2020).

  23. Dulio V, von der Ohe PC (2013) NORMAN Prioritisation framework for emerging substances (Accessible at https://www.norman-network.net/sites/default/files/files/Publications/NORMAN_prioritisation_Manual_15April2013_finalforwebsite-f.pdf. Last accessed 4 Feb 2020).

  24. Alygizakis NA, Besselink H, Paulus GK, Oswald P, Hornstra LM, Oswaldova M, et al. Characterization of wastewater effluents in the Danube River Basin with chemical screening, in vitro bioassays and antibiotic resistant genes analysis. Environ Int. 2019;127:420–9. https://doi.org/10.1016/j.envint.2019.03.060.

    Article  CAS  PubMed  Google Scholar 

  25. Encyclopedia NW. Chisinau. 2017. (Accessible at https://www.newworldencyclopedia.org/entry/Chisinau. Last accessed 4 Feb 2020).

  26. Lin C, He M, Zhou Y, Guo W, Yang Z. Distribution and contamination assessment of heavy metals in sediment of the Second Songhua River, China. Environ Monit Assess. 2008;137(1-3):329–42. https://doi.org/10.1007/s10661-007-9768-1.

    Article  CAS  PubMed  Google Scholar 

  27. Alygizakis NA, Gago-Ferrero P, Borova VL, Pavlidou A, Hatzianestis I, Thomaidis NS. Occurrence and spatial distribution of 158 pharmaceuticals, drugs of abuse and related metabolites in offshore seawater. Sci Total Environ. 2016;541:1097–105. https://doi.org/10.1016/j.scitotenv.2015.09.145.

    Article  CAS  PubMed  Google Scholar 

  28. United Nations Environment. Fake pesticides, real problems: addressing Ukraine’s illegal and counterfeit pesticides problem. 2018. (Accessible at https://www.unenvironment.org/news-and-stories/story/fake-pesticides-real-problems-addressing-ukraines-illegal-and-counterfeit, Last accessed 4 February 2020).

  29. Pryde P. Environmental Resources And Constraints In The Former Soviet Republics. 1995. (Accessible at https://books.google.gr/books/about/Environmental_Resources_And_Constraints.html?id=IqubDwAAQBAJ&source=kp_cover&redir_esc=y. Last accessed 4 Feb 2020).

  30. Kimstach V, Maeybeck M, Baroudy E. A Water Quality Assessment of the Former Soviet Union. 1998. (Accessible at https://books.google.gr/books?id=2dk_SC5TIl8C&lpg=PP1&dq=AWaterQualityAssessmentoftheFormerSovietUnion. Last accessed 4 Feb 2020).

  31. Cox L, Hermosin MC, Cornejo J, Mansour M. Photolysis of metamitron in water in the presence of soils and soil components. Chemosphere. 1996;33(10):2057–64. https://doi.org/10.1016/0045-6535(96)00297-4.

    Article  CAS  Google Scholar 

  32. Rivard L. Environmental Fate of Metolachlor Linda Rivard Environmental Monitoring Branch Department of Pesticide Regulation. 2003. (Accessible at https://www.semanticscholar.org/paper/Environmental-Fate-of-Metolachlor-Linda-Rivard-of-Rivard/6af152adb607b080f9065eeb22832b9c99027153. Last accessed 4 Feb 2020).

  33. Mudhoo A, Garg VK. Sorption, transport and transformation of atrazine in soils, minerals and composts: a review. Pedosphere. 2011;21(1):11–25. https://doi.org/10.1016/s1002-0160(10)60074-4.

    Article  CAS  Google Scholar 

  34. Lucas AD, Bekheit HKM, Goodrow MH, Jones D, Kullman S, Matsumura F, et al. Development of antibodies against hydroxyatrazine and hydroxysimazine: application to environmental samples. J Agric Food Chem. 1993;41:1523–9. https://doi.org/10.1021/jf00041a040.

    Article  CAS  Google Scholar 

  35. Guzzella L, Rullo S, Pozzoni F, Giuliano G. Studies on mobility and degradation pathways of tebuthylazine using lysimeters on a field scale. J Environ Qual. 2003;32:1089–98.

    Article  CAS  Google Scholar 

  36. Ghosh RK, Singh N. Leaching behaviour of azoxystrobin and metabolites in soil columns. Pest Manag Sci. 2009;65(9):1009–14. https://doi.org/10.1002/ps.1787.

    Article  CAS  PubMed  Google Scholar 

  37. Singh S, Singh N, Kumar V, Datta S, Wani AB, Singh D, et al. Toxicity, monitoring and biodegradation of the fungicide carbendazim. Environ Chem Lett. 2016;14(3):317–29. https://doi.org/10.1007/s10311-016-0566-2.

    Article  CAS  Google Scholar 

  38. Wiegel S, Aulinger A, Brockmeyer R, Harms H, Loffler J, Reincke H, et al. Pharmaceuticals in the river Elbe and its tributaries. Chemosphere. 2004;57(2):107–26. https://doi.org/10.1016/j.chemosphere.2004.05.017.

    Article  CAS  PubMed  Google Scholar 

  39. Garcia-Martin E, Esguevillas G, Blanca-Lopez N, Garcia-Menaya J, Blanca M, Amo G, et al. Genetic determinants of metamizole metabolism modify the risk of developing anaphylaxis. Pharmacogenet Genomics. 2015;25(9):462–4. https://doi.org/10.1097/FPC.0000000000000157.

    Article  CAS  PubMed  Google Scholar 

  40. Leclercq M, Mathieu O, Gomez E, Casellas C, Fenet H, Hillaire-Buys D. Presence and fate of carbamazepine, oxcarbazepine, and seven of their metabolites at wastewater treatment plants. Arch Environ Contam Toxicol. 2009;56(3):408–15. https://doi.org/10.1007/s00244-008-9202-x.

    Article  CAS  PubMed  Google Scholar 

  41. Slobodnik J, Alexandrov B, Komorin V, Mikaelyan A, Guchmanidze A, Arabidze M, Korshenko A, Moncheva S. National Pilot Monitoring Studies and Joint Open Sea Surveys in Georgia, Russian Federation and Ukraine, 2016. Final Scientific Report, EU/UNDP Project: Improving Environmental Monitoring in the Black Sea e Phase II (EMBLAS-II) ENPI/2013/313-169. 2016. (Accessible at http://emblasproject.org/wp-content/uploads/2017/04/Joint-Black-Sea-Surveys-2016_16.pdf. Last accessed 4 Feb 2020).

  42. Loos R, Marinov D, Sanseverino I, Napierska D, Lettieri T. Review of the 1st Watch List under the Water Framework Directive and recommendations for the 2nd Watch List. 2018. (Accessible at https://publications.jrc.ec.europa.eu/repository/bitstream/JRC111198/wl_report_jrc_2018_04_26_final_online.pdf. Last accessed 4 Feb 2020).

  43. Aalizadeh R, von der Ohe PC, Thomaidis NS. Prediction of acute toxicity of emerging contaminants on the water flea Daphnia magna by Ant Colony Optimization-Support Vector Machine QSTR models. Environ Sci Process Impacts. 2017;19(3):438–48. https://doi.org/10.1039/c6em00679e.

    Article  CAS  PubMed  Google Scholar 

  44. Hollender J, van Bavel B, Dulio V, Farmen E, Furtmann K, Koschorreck J, et al. High resolution mass spectrometry-based non-target screening can support regulatory environmental monitoring and chemicals management. Environ Sci Eur. 2019;31(1). https://doi.org/10.1186/s12302-019-0225-x.

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Acknowledgments

The authors would like to acknowledge OSCE Ukraine for financing the study, Ukrainian scientific center of Ecology of Sea in Odessa for support at sampling and sample transport logistics, and NORMAN network (https://www.norman-network.net/) for providing access to its latest version of the Ecotoxicology Database.

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Correspondence to Nikolaos S. Thomaidis.

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No vertebrate animals are used in the study. No violation of animal rights occurred during this investigation. The samples were collected after informed consent by the occupants of the premises sampled.

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The authors declare that they have no conflict of interest.

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Published in the topical collection Persistent and Mobile Organic Compounds – An Environmental Challenge with guest editors Torsten C. Schmidt, Thomas P. Knepper, and Thorsten Reemtsma.

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Diamanti, K.S., Alygizakis, N.A., Nika, MC. et al. Assessment of the chemical pollution status of the Dniester River Basin by wide-scope target and suspect screening using mass spectrometric techniques. Anal Bioanal Chem 412, 4893–4907 (2020). https://doi.org/10.1007/s00216-020-02648-y

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