Environmental Science and Pollution Research

, Volume 25, Issue 31, pp 31040–31050 | Cite as

Environmental exposure of anthropogenic micropollutants in the Prut River at the Romanian-Moldavian border: a snapshot in the lower Danube river basin

  • Zaharie Moldovan
  • Olivian Marincas
  • Igor Povar
  • Tudor Lupascu
  • Philipp Longree
  • Jelena Simovic Rota
  • Heinz Singer
  • Alfredo C. AlderEmail author
Research Article


The Prut River, the second longest tributary of the Danube river, was investigated for a wide range of anthropogenic organic pollutants to fill the data gap on environmental contamination in eastern European surface waters. In this study, the occurrence of a wide range of organic pollutants was measured along the transboundary Prut River, between Sculeni and Branza in 2010–2012. Using two different analytical methods, gas chromatography coupled to mass spectrometry and liquid chromatography coupled to high-resolution mass spectrometry, over 300 compounds were screened for and 88 compounds were determined in the Prut River. In general, the chemicals occurred at low levels. At the last sampling site upstream of the confluence with the Danube river at Branza, the highest average concentrations (≥ 100 ng L−1) were determined for the artificial sweetener acesulfame, the pharmaceuticals metformin, 4-acetamidoantipyrene, and 4,4,5,8-tetramethylchroman-2-ol, the antioxidants 2,4-di-tert-butylphenol, 3-tert-butyl-4-hydroxyanisol, and 3,5-di-tert-butyl-4-hydroxy-toluene, the personal care products HHCB (galaxolide), 4-phenyl-benzophenone, and octyl dimethyl-p-aminobenzoic acid, the industrial chemical diphenylsulfone, and the sterol cholesterol. Low concentrations of agricultural pesticides occurred in the catchment. At Branza, the total accumulated load of all measured compounds was calculated to be almost 19 kg day−1. In comparison to the Rhine River, the loads in the Prut, determined with same LC-HRMS method for the same set of analytes, were two orders of magnitude lower. Discharge of wastewater without proper treatment from the city of Iasi in the Jijia catchment (Romania) as well as from the city of Cahul (Moldova) revealed a distinct increase in concentrations and loads in the Prut at Frasinesti and Branza. Thus, an implementation of wastewater treatment capacities in the Prut River basin would considerably reduce the loads of micropollutants from urban point sources.


Prut River catchment Target screening Organic pollutants River monitoring GC-MS LC-HRMS 



Jennifer Schollee and Urs Schönenberger are acknowledged for their valuable comments on the manuscript.

Funding information

The study was funded by the Scientific Cooperation between Eastern Europe and Switzerland Program (SCOPES) of the Swiss National Science Foundation, project IZ73Z0 128036/1.

Supplementary material

11356_2018_3025_MOESM1_ESM.docx (124 kb)
ESM 1 (DOCX 123 kb)
11356_2018_3025_MOESM2_ESM.xlsx (56 kb)
ESM 2 (XLSX 55 kb)


  1. Andresen JA, Grundmann A, Bester K (2004) Organophosphorus flame retardants and plasticisers in surface waters. Sci Total Environ 332:155–166CrossRefGoogle Scholar
  2. Antic N, Radisic M, Radovic T, Vasiljevic T, Grujic S, Petkovic A, Dimkic M, Lausevic M (2015) Pesticide residues in the Danube River Basin in Serbia—a survey during 2009-2011. Clean-Soil Air Water 43:197–204CrossRefGoogle Scholar
  3. Bacaloni A, Cavaliere C, Foglia P, Nazzari M, Samperi R, Lagana A (2007) Liquid chromatography/tandem mass spectrometry determination of organophosphorus flame retardants and plasticizers in drinking and surface waters. Rapid Commun Mass Spectrom 21:1123–1130CrossRefGoogle Scholar
  4. Bendz D, Paxéus NA, Ginn TR, Loge FJ (2005) Occurrence and fate of pharmaceutically active compounds in the environment, a case study: Höje River in Sweden. J Hazard Mater 122:195–204CrossRefGoogle Scholar
  5. Bentayeb K, Ackerman LK, Lord T, Begley TH (2013) Non-visible print set-off of photoinitiators in food packaging: detection by ambient ionisation mass spectrometry. Food Addit Contam Part A Chem Anal Control Expo Risk Assess 30:750–759CrossRefGoogle Scholar
  6. Bollmann UE, Moler A, Xie ZY, Ebinghaus R, Einax JW (2012) Occurrence and fate of organophosphorus flame retardants and plasticizers in coastal and marine surface waters. Water Res 46:531–538CrossRefGoogle Scholar
  7. Brausch JM, Rand GM (2011) A review of personal care products in the aquatic environment: environmental concentrations and toxicity. Chemosphere 82:1518–1532CrossRefGoogle Scholar
  8. Brooke DN, Burns JS, Crookes MJ (2008) UV-filters in cosmetics—prioritisation for environmental assessment, Environment Agency, Bristol, UK. Accessed 2/21/2018
  9. Buerge IJ, Buser HR, Kahle M, Muller MD, Poiger T (2009) Ubiquitous occurrence of the artificial sweetener acesulfame in the aquatic environment: an ideal chemical marker of domestic wastewater in groundwater. Environmental Science & Technology 43:4381–4385CrossRefGoogle Scholar
  10. Castronovo S, Wick A, Scheurer M, Nödler K, Schulz M, Ternes TA (2017) Biodegradation of the artificial sweetener acesulfame in biological wastewater treatment and sandfilters. Water Res 110:342–353CrossRefGoogle Scholar
  11. Cerna A, Cibulkova Z, Simon P, Uhlar J, Lehocky P (2012) DSC study of selected antioxidants and their binary mixtures in styrene-butadiene rubber. Polym Degrad Stab 97:1724–1729CrossRefGoogle Scholar
  12. Chitescu CL, Kaklamanos G, Nicolau AI, Stolker AAM (2015) High sensitive multiresidue analysis of pharmaceuticals and antifungals in surface water using U-HPLC-Q-Exactive Orbitrap HRMS. Application to the Danube river basin on the Romanian territory. Sci Total Environ 532:501–511CrossRefGoogle Scholar
  13. Clara M, Strenn B, Kreuzinger N (2004) Carbamazepine as a possible anthropogenic marker in the aquatic environment: investigations on the behaviour of carbamazepine in wastewater treatment and during groundwater infiltration. Water Res 38:947–954CrossRefGoogle Scholar
  14. Cristale J, Katsoyiannis A, Sweetman AJ, Jones KC, Lacorte S (2013a) Occurrence and risk assessment of organophosphorus and brominated flame retardants in the River Aire (UK). Environ Pollut 179:194–200CrossRefGoogle Scholar
  15. Cristale J, Vazquez AG, Barata C, Lacorte S (2013b) Priority and emerging flame retardants in rivers: occurrence in water and sediment, Daphnia magna toxicity and risk assessment. Environ Int 59:232–243CrossRefGoogle Scholar
  16. Cuderman P, Heath E (2007) Determination of UV filters and antimicrobial agents in environmental water samples. Anal Bioanal Chem 387:1343–1350CrossRefGoogle Scholar
  17. del Nogal Sánchez M, Glanzer P, Pérez Pavón J, García Pinto C, Moreno Cordero B (2010) Determination of antioxidants in new and used lubricant oils by headspace-programmed temperature vaporization–gas chromatography–mass spectrometry. Anal Bioanal Chem 398:3215–3224CrossRefGoogle Scholar
  18. Ekpeghere KI, Kim U-J, O S-H, Kim H-Y, Oh J-E (2016) Distribution and seasonal occurrence of UV filters in rivers and wastewater treatment plants in Korea. Sci Total Environ 542(Part A):121–128CrossRefGoogle Scholar
  19. EPIRB (2015) (Environmental Protection of International River Basins), Prut River Basin Management Plan 2016–2021. Institute of Ecology and Geography of the Academy of Sciences of Moldova, Accessed 2/21/2018
  20. EU (2013) European Union Directive 2013/39/EU of the European Parliament and of the Council. Accessed 2/21/2018
  21. Fries E, Puttmann W (2002) Analysis of the antioxidant butylated hydroxytoluene (BHT) in water by means of solid phase extraction combined with GC/MS. Water Res 36:2319–2327CrossRefGoogle Scholar
  22. Gallart-Ayala H, Núñez O, Moyano E, Galceran MT (2011) Analysis of UV ink photoinitiators in packaged food by fast liquid chromatography at sub-ambient temperature coupled to tandem mass spectrometry. J Chromatogr A 1218:459–466CrossRefGoogle Scholar
  23. Gunalan G, Vijayalakshmi K, Saraswathy A, Hopper W, Tamilvannan T (2014) Anti-inflammatory activities of phytochemicals from Bauhinia variegata Linn. leaf: an in silico approach. J Chem Pharm Res 6:334–348Google Scholar
  24. Heeb F, Singer H, Pernet-Coudrier B, Qi WX, Liu HJ, Longree P, Muller B, Berg M (2012) Organic micropollutants in rivers downstream of the megacity Beijing: sources and mass fluxes in a large-scale wastewater irrigation system. Environ Sci Technol 46:8680–8688CrossRefGoogle Scholar
  25. Jenke D (2003) Chromatographic methods used to identify and quantify organic polymer additives (reprinted from encyclopedia of chromatography, 2003). J Liq Chromatogr Relat Technol 26:2417–2447CrossRefGoogle Scholar
  26. Jensen KR, Voorhees KJ, Dempsey EA, Burton J, Ratcliff MA, McCormick RL (2014) Formation of 2,6-di-tert-butyl-4-nitrophenol during combustion of diesel fuel antioxidant precursors. Energy Fuel 28:7038–7042CrossRefGoogle Scholar
  27. Kahl S, Kleinsteuber S, Nivala J, van Afferden M, Reemtsma T (2018) Emerging biodegradation of the previously persistent artificial sweetener acesulfame in biological wastewater treatment. Environ Sci Technol 52:2717–2725CrossRefGoogle Scholar
  28. Kern S, Fenner K, Singer HP, Schwarzenbach RP, Hollender J (2009) Identification of transformation products of organic contaminants in natural waters by computer-aided prediction and high-resolution mass spectrometry. Environ Sci Technol 43:7039–7046CrossRefGoogle Scholar
  29. Kolpin DW, Skopec M, Meyer MT, Furlong ET, Zaugg SD (2004) Urban contribution of pharmaceuticals and other organic wastewater contaminants to streams during differing flow conditions. Sci Total Environ 328:119–130CrossRefGoogle Scholar
  30. Krymkin NY, Shakun VA, Nesterova TN, Naumkin PV, Shuraev MV (2016) Theory and practice of alkyl phenol synthesis. tert-octylphenols. Ind Eng Chem Res 55:9829–9839CrossRefGoogle Scholar
  31. Lange C, Kuch B, Metzger JW (2015) Occurrence and fate of synthetic musk fragrances in a small German river. J Hazard Mater 282:34–40CrossRefGoogle Scholar
  32. Liška I, Wagner F, Sengl M, Deutsch K, Slobodník J (2015) Joint Danube Survey 3: a comprehensive analysis of Danube water quality. ICPDR – International Commission for the Protection of the Danube River., Vienna (Austria). Accessed 7/7/2018
  33. Loos R, Gawlik BM, Boettcher K, Locoro G, Contini S, Bidoglio G (2009a) Sucralose screening in European surface waters using a solid-phase extraction-liquid chromatography-triple quadrupole mass spectrometry method. J Chromatogr A 1216:1126–1131CrossRefGoogle Scholar
  34. Loos R, Gawlik BM, Locoro G, Rimaviciute E, Contini S, Bidoglio G (2009b) EU-wide survey of polar organic persistent pollutants in European river waters. Environ Pollution 157:561–568CrossRefGoogle Scholar
  35. Loos R, Locoro G, Contini S (2010) Occurrence of polar organic contaminants in the dissolved water phase of the Danube River and its major tributaries using SPE-LC-MS2 analysis. Water Res 44:2325–2335CrossRefGoogle Scholar
  36. Loos R, Tavazzi S, Mariani G, Suurkuusk G, Paracchini B, Umlauf G (2017) Analysis of emerging organic contaminants in water, fish and suspended particulate matter (SPM) in the Joint Danube Survey using solid-phase extraction followed by UHPLC-MS-MS and GC–MS analysis. Sci Total Environ 607-608:1201–1212CrossRefGoogle Scholar
  37. Loschner D, Rapp T, Schlosser FU, Schuster R, Stottmeister E, Zander S (2011) Experience with the application of the draft European Standard prEN 15768 to the identification of leachable organic substances from materials in contact with drinking water by GC-MS. Anal Methods 3:2547–2556CrossRefGoogle Scholar
  38. Lutzhoft HCH, Waul CK, Andersen HR, Seredynska-Sobecka B, Mosbaek H, Christensen N, Olsson ME, Arvin E (2013) HS-SPME-GC-MS analysis of antioxidant degradation products migrating to drinking water from PE materials and PEX pipes. Int J Environ Anal Chem 93:593–612CrossRefGoogle Scholar
  39. Martinez-Carballo E, Gonzalez-Barreiro C, Sitka A, Scharf S, Gans O (2007) Determination of selected organophosphate esters in the aquatic environment of Austria. Sci Total Environ 388:290–299CrossRefGoogle Scholar
  40. Moldovan Z, Schmutzer G, Tusa F, Calin R, Alder AC (2007) An overview of pharmaceuticals and personal care products contamination along the river Somes watershed, Romania. J Environ Monit 9:986–993CrossRefGoogle Scholar
  41. Moldovan Z, Chira R, Alder AC (2009) Environmental exposure of pharmaceuticals and musk fragrances in the Somes River before and after upgrading the municipal wastewater treatment plant Cluj-Napoca, Romania. Environ Sci Pollut Res 16:46–54CrossRefGoogle Scholar
  42. OECD (1995) Phenol, 4-(1,1,3,3-tetramethylbutyl)-; Accessed 2/21/2018
  43. Oekotoxzentrum (2016) Swiss Centre for Applied Ecotoxicolog; Accessed 2/21/2018
  44. OSPAR Comission (2008) Towards the cessation target: emissions, discharges and losses of OSPAR chemicals identified for priority action; and Accessed 2/21/2018
  45. OSPAR Commission (2006) 4-(dimethylbutylamino)diphenylamine (6PPD); Hazardous Substances Series; and Accessed 2/21/2018
  46. Quednow K, Puttmann W (2009) Temporal concentration changes of DEET, TCEP, terbutryn, and nonylphenols in freshwater streams of Hesse, Germany: possible influence of mandatory regulations and voluntary environmental agreements. Environ Sci Pollut Res 16:630–640CrossRefGoogle Scholar
  47. Radjenovic J, Pereza S, Petrovic M, Barcelo D (2008) Identification and structural characterization of biodegradation products of atenolol and glibenclamide by liquid chromatography coupled to hybrid quadrupole time-of-flight and quadrupole ion trap mass spectrometry. J Chromatogr A 1210:142–153CrossRefGoogle Scholar
  48. Ramos S, Homem V, Alves A, Santos L (2015) Advances in analytical methods and occurrence of organic UV-filters in the environment—a review. Sci Total Environ 526:278–311CrossRefGoogle Scholar
  49. Regnery J, Puettmann W (2010) Occurrence and fate of organophosphorus flame retardants and plasticizers in urban and remote surface waters in Germany. Water Res 44:4097–4104CrossRefGoogle Scholar
  50. Rial E, Rodríguez-Sánchez L, Aller P, Guisado A, Mar González-Barroso M, Gallardo-Vara E, Redondo-Horcajo M, Castellanos E, Fernández de la Pradilla R, Viso A (2011) Development of chromanes as novel inhibitors of the uncoupling proteins. Chem Biol 18:264–274CrossRefGoogle Scholar
  51. Rodil R, Moeder M, Altenburger R, Schmitt-Jansen M (2009) Photostability and phytotoxicity of selected sunscreen agents and their degradation mixtures in water. Anal Bioanal Chem 395:1513–1524CrossRefGoogle Scholar
  52. Rodil R, Quintana JB, Basaglia G, Pietrogrande MC, Cela R (2010) Determination of synthetic phenolic antioxidants and their metabolites in water samples by downscaled solid-phase extraction, silylation and gas chromatography–mass spectrometry. J Chromatogr A 1217:6428–6435CrossRefGoogle Scholar
  53. Rodil R, Benito Quintana J, Cela R (2012) Oxidation of synthetic phenolic antioxidants during water chlorination. J Hazard Mater 199:73–81CrossRefGoogle Scholar
  54. Roots O, Roose A (2013) Hazardous substances in the aquatic environment in Estonia. Chemosphere 93:196–200CrossRefGoogle Scholar
  55. Ruff M, Mueller MS, Loos M, Singer HP (2015) Quantitative target and systematic non-target analysis of polar organic micro-pollutants along the river Rhine using high-resolution mass-spectrometry—identification of unknown sources and compounds. Water Res 87:145–154CrossRefGoogle Scholar
  56. Rusu V, Postolachi L, Povar I, Alder AC, Lupascu T (2012) Dynamics of phosphorus forms in the bottom sediments and their interstitial water for the Prut River (Moldova). Environ Sci Pollut Res 19:3126–3131CrossRefGoogle Scholar
  57. Sakkas VA, Giokas DL, Lambropoulou DA, Albanis TA (2003) Aqueous photolysis of the sunscreen agent octyl-dimethyl-p-aminobenzoic acid: formation of disinfection byproducts in chlorinated swimming pool water. J Chromatogr A 1016:211–222CrossRefGoogle Scholar
  58. Sánchez-Quiles D, Tovar-Sánchez A (2015) Are sunscreens a new environmental risk associated with coastal tourism? Environ Int 83:158–170CrossRefGoogle Scholar
  59. Sapozhnikova Y, Zubcov N, Hungerford S, Roy LA, Boicenco N, Zubcov E, Schlenk D (2005) Evaluation of pesticides and metals in fish of the Dniester River, Moldova. Chemosphere 60:196–205CrossRefGoogle Scholar
  60. Scheurer M, Brauch HJ, Lange FT (2009) Analysis and occurrence of seven artificial sweeteners in German waste water and surface water and in soil aquifer treatment (SAT). Anal Bioanal Chem 394:1585–1594CrossRefGoogle Scholar
  61. Scheurer M, Storck FR, Graf C, Brauch H-J, Ruck W, Lev O, Lange FT (2011) Correlation of six anthropogenic markers in wastewater, surface water, bank filtrate, and soil aquifer treatment. J Environ Monit 13:966–973CrossRefGoogle Scholar
  62. Schwarzenbach RP, Gschwend PM, Imboden DM (2003) Environmental organic chemistry. Wiley-Interscience, New YorkGoogle Scholar
  63. Shepherd K (2011) Highlighting the stories of the Prut. Danube Watch 1, 26–27. Accessed 2/21/2018
  64. Singh SP, Azua A, Chaudhary A, Khan S, Willett KL, Gardinali PR (2010) Occurrence and distribution of steroids, hormones and selected pharmaceuticals in South Florida coastal environments. Ecotoxicology 19:338–350CrossRefGoogle Scholar
  65. Skjevrak I, Due A, Gjerstad KO, Herikstad H (2003) Volatile organic components migrating from plastic pipes (HDPE, PEX and PVC) into drinking water. Water Res 37:1912–1920CrossRefGoogle Scholar
  66. Skjevrak I, Lund V, Ormerod K, Herikstad H (2005) Volatile organic compounds in natural biofilm in polyethylene pipes supplied with lake water and treated water from the distribution network. Water Res 39:4133–4141CrossRefGoogle Scholar
  67. Tran NH, Hu JY, Li JH, Ong SL (2014) Suitability of artificial sweeteners as indicators of raw wastewater contamination in surface water and groundwater. Water Res 48:443–456CrossRefGoogle Scholar
  68. Tsui MMP, Leung HW, Wai T-C, Yamashita N, Taniyasu S, Liu W, Lam PKS, Murphy MB (2014) Occurrence, distribution and ecological risk assessment of multiple classes of UV filters in surface waters from different countries. Water Res 67:55–65CrossRefGoogle Scholar
  69. van der Veen I, de Boer J (2012) Phosphorus flame retardants: properties, production, environmental occurrence, toxicity and analysis. Chemosphere 88:1119–1153CrossRefGoogle Scholar
  70. Wang J-Z, Guan Y-F, Ni H-G, Liu G-J, Zeng EY (2010) Fecal steroids in riverine runoff of the Pearl River Delta, South China: levels, potential sources and inputs to the coastal ocean. J Environ Monit 12:280–286CrossRefGoogle Scholar
  71. Wei GL, Li DQ, Zhuo MN, Liao YS, Xie ZY, Guo TL, Li JJ, Zhang SY, Liang ZQ (2015) Organophosphorus flame retardants and plasticizers: sources, occurrence, toxicity and human exposure. Environ Pollut 196:29–46CrossRefGoogle Scholar
  72. Wolschke H, Sühring R, Xie Z, Ebinghaus R (2015) Organophosphorus flame retardants and plasticizers in the aquatic environment: a case study of the Elbe River, Germany. Environ Pollut 206:488–493CrossRefGoogle Scholar
  73. Yang Y-Y, Liu W-R, Liu Y-S, Zhao J-L, Zhang Q-Q, Zhang M, Zhang J-N, Jiang Y-X, Zhang L-J, Ying G-G (2017) Suitability of pharmaceuticals and personal care products (PPCPs) and artificial sweeteners (ASs) as wastewater indicators in the Pearl River Delta, South China. Sci Total Environ 590–591:611–619CrossRefGoogle Scholar
  74. Zhang Z, Lei Z, Zhang Z, Sugiura N, Xu X, Yin D (2007) Organics removal of combined wastewater through shallow soil infiltration treatment: a field and laboratory study. J Hazard Mater 149:657–665CrossRefGoogle Scholar
  75. Zygoura PD, Paleologos EK, Kontominas MG (2011) Effect of ionising radiation treatment on the specific migration characteristics of packaging-food simulant combinations: effect of type and dose of radiation. Food Addit Contam Part A Chem Anal Control Expo Risk Assess 28:686–694CrossRefGoogle Scholar

Copyright information

© Springer-Verlag GmbH Germany, part of Springer Nature 2018

Authors and Affiliations

  • Zaharie Moldovan
    • 1
  • Olivian Marincas
    • 1
  • Igor Povar
    • 2
  • Tudor Lupascu
    • 2
  • Philipp Longree
    • 3
  • Jelena Simovic Rota
    • 3
  • Heinz Singer
    • 3
  • Alfredo C. Alder
    • 3
    Email author
  1. 1.National Institute for Research and Development of Isotopic and Molecular TechnologyCluj-NapocaRomania
  2. 2.Academy of Sciences of Moldova, Institute of ChemistryChisinauRepublic of Moldova
  3. 3.Eawag, Swiss Federal Institute of Aquatic Science and TechnologyDübendorfSwitzerland

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