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A multi-residue method for determination of 70 organic micropollutants in surface waters by solid-phase extraction followed by gas chromatography coupled to tandem mass spectrometry

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Abstract

A multi-residue method, based on gas chromatography coupled to tandem mass spectrometry (GC-MS/MS), has been developed for the determination of 70 organic micropollutants from various chemical classes (organochlorinated, organophosphorous, triazines, carbamate and urea, polycyclic aromatic hydrocarbons, polychlorinated biphenyls, pharmaceuticals, phenols, etc.) in surface waters. A single-step SPE extraction using OASIS HLB cartridges was employed for the recovery of target micropollutants. The method has been validated according to monitoring performance criteria of the Water Framework Directive, taking into account the approved guidelines on quality assurance and quality control. The recoveries ranged from 60 to 110 %, the coefficient of variation from 0.84 to 27.4 %, and the uncertainty from 6 to 37 %. The LOD varied from 6.0 to 40 ng/L. The limits of quantification for the priority pollutants anthracene, alachlor, atrazine, benzo(a)pyrene, chlorfenvinphos, diuron, isoproturon, nonylphenol, simazine, and terbutryn fulfill the criterion of <30 % of the relevant environmental standards. The method was employed to investigate the water quality in the basin of a transboundary river, Strymonas, in NE Greece during three sampling campaigns conducted in the year 2013. Thirty-nine compounds were detected in the river water. Metolachlor, diuron, isoproturon, salicylic acid, chlorfenvinphos, 1,2-benzanthracene, pyrene, diflubenzuron, and carbaryl exhibited the highest detection frequencies.

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References

  • APHA, AWWA, WPCF (1995) Standard methods for the examination of water and wastewater, 19th ed. American Public Health Association, Washington

  • Arditsoglou A, Voutsa D (2008a) Determination of phenolic and steroid endocrine disrupting compounds in environmental matrices. Environ Sci Pollut Res 15(3):228–236

    Article  CAS  Google Scholar 

  • Arditsoglou A, Voutsa D (2008b) Passive sampling of selected endocrine disrupting compounds using polar organic chemical integrative samplers. Environ Pollut 156:316–324

    Article  CAS  Google Scholar 

  • Arditsoglou A, Voutsa D (2010) Partitioning of endocrine disrupting compounds in inland waters and wastewaters discharged into the coastal area of Thessaloniki, Northern Greece. Environ Sci Pollut Res 17:529–538

    Article  CAS  Google Scholar 

  • Azevedo DA, Lacorte S, Vinhas T, Viana P, Barcelo D (2000) Monitoring of priority pesticides and other organic pollutants in river water from Portugal by gas chromatography–mass spectrometry and liquid chromatography-atmospheric pressure chemical ionization mass spectrometry. J Chromatogr A 879:13–26

    Article  Google Scholar 

  • Barrek S, Cren-Olive C, Wiest L, Baudot R, Arnaudguilhem C, Grenier-Loustalot MF (2009) Multi-residue analysis and ultra-trace quantification of 36 priority substances from the European Water Framework Directive by GC-MS and LC-FLD-MS/MS in surface waters. Talanta 79:712–722

    Article  CAS  Google Scholar 

  • Botta F, Fauchon N, Blanchoud H, Chevreuil M, Guery B (2012) Phyt’Eaux Cites: application and validation of a programme to reduce surface water contamination with urban pesticides. Chemosphere 86:166–176

    Article  CAS  Google Scholar 

  • Brown CD, Beinum WV (2009) Pesticide transport via sub-surface drains in Europe. Environ Pollut 157:1–11

    Article  Google Scholar 

  • Canadian Ministry of the Environment, Laboratory Services Branch (2011) Protocol for analytical methods used in the assessment of properties under Part XV.1 of the Environmental Protection Act (O.Reg. 153/04), Ontario

  • Chalkidis I, Papadimos D (2007) Strymonas basin integrated surface water & groundwater model, phase i, input data and model set up, Technical report of LIFE, Greek Biotope/Wetland Centre, p.56

  • Cherta L, Beltran J, Portoles T, Hernandez F (2012) Multiclass determination of 66 organic micropollutants in environmental water samples by fast gas-chromatography-mass spectrometry. Anal Bioanal Chem 402:2301–2314

    Article  CAS  Google Scholar 

  • Cortada C, Vidal L, Tejada S, Romo A, Canals A (2009) Determination of organochlorine pesticides in complex matrices by single-drop microextraction coupled to gas chromatography–mass spectrometry. Anal Chim Acta 638:29–35

    Article  CAS  Google Scholar 

  • EC (1976) European Commission Directive 76/464/EC on pollution caused by certain dangerous substances discharged into the aquatic environment of the Community, Off J Eur Commun L 129/23

  • EC (2000) European Commission Directive 2000/60/EC establishing a framework for Community action in the field of water policy, Off J Eur Commun L 327/1

  • EC (2002) European Commission Decision No 657/2002 implementing Council Directive 96/23/EC concerning the performance of analytical methods and the interpretation of results, Off J Eur Commun L221/8

  • EC (2006) European Commission Directive 2006/11/EC on pollution caused by certain dangerous substances discharged into the aquatic environment of the Community, Off J Eur Commun L 64/52

  • EC (2008) European Commission Directive 2008/105/EC on environmental quality standards in the field of water policy, amending and subsequently repealing Council Directives 82/176/EEC, 83/513/EEC, 84/156/EEC, 84/491/EEC, 86/280/EEC and amending Directive 2000/60/EC of the European Parliament and of the Council, Off J Eur Commun L 348/84

  • EC (2009) European Commission Directive 2009/90/EC laying down, pursuant to Directive 2000/60/EC of the European Parliament and of the Council, technical specifications for chemical analysis and monitoring of water status, Off J Eur Commun L 201//36

  • EC (2013) European Commission Directive 2013/39/EC of the European Parliament and of the Council amending Directives 2000/60/EC and 2008/105/EC as regards priority substances in the field of water policy

  • EC Guidance (2009) Guidance Document No. 19 on surface water chemical monitoring under the Water Framework Directive, Technical Report – 2009 – 025

  • Gasperi J, Garnaud S, Rocher V, Moilleron R (2009) Priority pollutants in surface waters and settleable particles within a densely urbanised area: case study of Paris (France). Sci Total Environ 407:2900–2908

    Article  CAS  Google Scholar 

  • Greek Ministry of Environment, Energy & Climate change, Special Secretariat of Water (2014). http://wfd.opengov.gr/index.php?option=com_content&task=view&id=65&Itemid=12. Accessed January 2014

  • Gros M, Petrovic M, Barcelo D (2006) Development of a multi-residue analytical methodology based on liquid chromatography tandem mass spectrometry (LC-MS/MS) for screening and trace level determination of pharmaceuticals in surface and wastewaters. Talanta 70:678–690

    Article  CAS  Google Scholar 

  • Hilderbrandt A, Guillamon M, Lacorte S, Tauler R, Barcelo D (2008) Impact of pesticides used in agriculture and vineyards to surface and groundwater quality (North Spain). Water Res 42:3315–3326

    Article  Google Scholar 

  • ISO (1994) ISO 5725–3: Accuracy (trueness and precision) of measurement methods and results-Part 3: intermediate measures of the precision of a standard measurement method, ISO standards, ICS 03.120 30 (1994) 1

  • Jablonowski ND, Schaffer A, Burauel P (2011) Still present after all these years: persistence plus potential toxicity raise questions about the use of atrazine. Environ Sci Pollut Res 18:328–331

    Article  CAS  Google Scholar 

  • Kaklamanos G, Vincent U, Holst CV (2013) Analysis of antimicrobial agents in pig feet by liquid chromatography coupled to orbitrap mass spectrometry. J Chromatogr A 1290:60–74

    Article  Google Scholar 

  • Klosterhaus S, Grace R, Hamilton MC, Yee D (2013) Method validation and reconnaissance of pharmaceuticals, personal care products, and alkylphenols in surface waters, sediments, and mussels in an urban estuary. Environ Int 54:92–99

    Article  CAS  Google Scholar 

  • Kneeper TP (2004) Analysis and mass spectrometric characterization of the insect repellent Bayrepel and its main metabolite Bayrepel-acid. J Chromatogr A 1046:159–166

    Google Scholar 

  • Köck-Schulmeyer M, Ginebreda A, González S, Cortina JL, López de Alda M, Barceló D (2012) Analysis of the occurrence and risk assessment of polar pesticides in the Llobregat River Basin (NE Spain). Chemosphere 86:8–16

    Article  Google Scholar 

  • Konieczka P, Namieśnik J (2009) Estimating uncertainty in analytical procedures based on chromatographic techniques. J Chromatogr A 1217:882–891

    Article  Google Scholar 

  • Konstantinou I, Hela D, Albanis T (2006) The status of pesticide pollution in surface waters (rivers and lakes) of Greece. Part I. Review on occurrence and levels. Environ Pollut 141:555–570

    Article  CAS  Google Scholar 

  • Lavagnini I, Magno F (2006) A statistical overview on univariate calibration, inverse regression, and detection limits: application to gas chromatography/mass spectrometry technique. Mass Spectrom Rev 26:1–18

  • Lekkas T, Kolokythas G, Nikolaou A, Kostopoulou M, Kotrikla A, Gatidou G, Thomaidis NS et al (2004) Evaluation of the pollution of the surface waters of Greece from the priority compounds of List II, 76/464/EEC Directive, and other toxic compounds. Environ Int 30:995–1007

    Article  CAS  Google Scholar 

  • Lepom P, Brown B, Hanke G, Loos R, Quevauviller P, Wollgast J (2009) Needs for reliable analytical methods for monitoring chemical pollutants in surface water under the European Water Framework Directive. J Chromatogr A 1216:302–315

    Article  CAS  Google Scholar 

  • Lissalde S, Mazzella N, Fauvelle V, Delmas F, Mazellier P, Legube B (2011) Liquid chromatography coupled with tandem mass spectrometry method for thirty-three pesticides in natural water and comparison of performance between classical solid phase extraction and passive sampling approaches. J Chromatogr A 1218:1492–1502

    Article  CAS  Google Scholar 

  • Loos R, Gawlik BM, Locoro G, Rimaviciute E, Contini S, Bidiglio G (2009) EU-wide survey of polar organic persistent pollutants in European river waters. Environ Pollut 157:561–568

    Article  CAS  Google Scholar 

  • Miller JN, Miller JC (2005) Statistics and Chemometrics in Analytical Chemistry 5th edition. Pearson Education Limited, England

    Google Scholar 

  • Navarro A, Tauler R, Lacorte S, Barcelo D (2010) Occurrence and transport of pesticides and alkylphenols in water samples along the Ebro River Basin. J Hydrol 383:18–29

    Article  CAS  Google Scholar 

  • Nödler K, Licha T, Bester K, Sauter M (2010) Development of a multi-residue analytical method, based on liquid chromatography-tandem mass spectrometry, for the simultaneous determination of 46 micro-contaminants in aqueous samples. J Chromatogr A 1217:6511–6521

    Article  Google Scholar 

  • Nödler K, Licha T, Voutsa D (2013) Twenty years later-Atrazine concentrations in selected coastal waters of the Mediterranean and the Baltic Sea. Mar Pollut Bull 70:112–118

    Article  Google Scholar 

  • Palma P, Alvarenga P, Palma V, Matos C, Fernandes RM, Soares A, Barbosa IR (2010) Evaluation of surface water quality using an ecotoxicological approach : a case study of the Alqueva Reservoir (Portugal). Environ Sci Pollut Res 17:703–716

    Article  CAS  Google Scholar 

  • Palma P, Köck-Schulmeyer M, Alvarenga P, Ledo L, Barbosa IR, López de Alda M, Barceló D (2014) Risk assessment of pesticides detected in surface water of the Alqueva reservoir (Guadiana basin, southern of Portugal). Sci Total Environ 488–489:208–219

    Article  Google Scholar 

  • Peng X, Yu Y, Tang C, Tan J, Huang Q, Wang Z (2008) Occurrence of steroid estrogens, endocrine-disrupting phenols, and acid pharmaceutical residues in urban riverine water of the Pearl River Delta, South China. Sci Total Environ 397:158–166

    Article  CAS  Google Scholar 

  • Pitarch E, Medina C, Portolés T, López FJ, Hernández F (2007) Determination of priority organic micro-pollutants by gas chromatography coupled to triple quadropole mass spectrometry. Anal Chim Acta 583:246–258

    Article  CAS  Google Scholar 

  • Quintana JB, Rodil R, Lorenzo SM, Mahia PL, Rodriguez DP (2007) Multiresidue analysis of acidic and polar organic contaminants in water samples by stir-bar sorptive extraction-liquid desorption-gas chromatography–mass spectrometry. J Chromatogr A 1174:27–39

    Article  CAS  Google Scholar 

  • Robles-Molina J, Gilbert-López B, García-Reyes JF, Molina-Díaz A (2013) Comparative evaluation of liquid-liquid extraction, solid-phase extraction and solid-phase microextraction for gas chromatography–mass spectrometry determination of multiclass priority organic contaminants in wastewater. Talanta 117:382–391

    Article  CAS  Google Scholar 

  • Robles-Molina J, Gilbert-López B, García-Reyes JF, Molina-Díaz A (2014) Monitoring of selected priority and emerging contaminants in the Guadalquivir River and other related surface waters in the province of Jaén, South East Spain. Sci Total Environ 479–480:247–257

    Article  Google Scholar 

  • Sanchez-Avila J, Bonet J, Velasco G, Lacorte S (2009) Determination and occurrence of phthalates, alkylphenols, bisphenol A, PBDEs, PCBs and PAHs in an industrial sewage grid discharging to a municipal wastewater treatment plant. Sci Total Environ 407:4157–4167

    Article  CAS  Google Scholar 

  • Scott PD, Bartkow M, Blockwell SJ, Coleman HM, Khan SJ, Lim R, McDonald JA, Nice H, Nugegoda D, Pettigrove V, Tremblay LA, Warne M, Leusch FDL (2014) An assessment of endocrine activity in Australian rivers using chemical and in vitro analyses. Environ Sci Pollut Res Int. doi:10.1007/s11356-014-3235-7

  • Sebok A, Vasanits-Zsigrai A, Helenkar A, Zaray G, Molnar-Perl I (2009) Multiresidue analysis of pollutants as their trimethylsilyl derivatives, by gas chromatography–mass spectrometry. J Chromatogr A 1216:2288–2301

    Article  CAS  Google Scholar 

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

    Article  CAS  Google Scholar 

  • Singer H, Jaus S, Hanke I, Luck A, Hollender J, Alder AC (2010) Determination of biocides and pesticides by on-line solid phase extraction coupled with mass spectrometry and their behaviour in wastewater and surface water. Environ Pollut 158:3054–3064

    Article  CAS  Google Scholar 

  • Smital T, Terzić S, Lončar J, Senta I, Žaja R, Popović M, Mikac I, Tollefsen KA, Thomas KV, Ahel M (2013) Prioritisation of organic contaminants in a river basin using chemical analyses and bioassays. Environ Sci Pollut Res 20:1384–1395

    Article  CAS  Google Scholar 

  • Steene JCV, Stove CP, Lambert WE (2010) A field study on 8 pharmaceuticals and 1 pesticide in Belgium: removal rates in waste water treatment plants and occurrence in surface water. Sci Total Environ 408:3448–3453

    Article  Google Scholar 

  • Terzić S, Senta I, Ahel M, Gros M, Petrović M, Barcelo D, Muller J et al (2008) Occurrence and fate of emerging wastewater contaminants in Western Balkan Region. Sci Total Environ 399:66–77

    Article  Google Scholar 

  • Terzopoulou E, Voutsa D (2014) Quality assessment of surface waters at the basin of Strymonas River, Northern Greece. Environ Monit. Assess (under reviewing process)

  • Tran NH, Hu J, Ong SL (2013) Simultaneous determination of PPCPs, EDCs, and artificial sweeteners in environmental water samples using a single-step SPE coupled with HPLC-MS/MS and isotope dilution. Talanta 113:82–92

    Article  CAS  Google Scholar 

  • Tran NH, Li J, Hi J, Ong SL (2014) Occurrence and suitability of pharmaceuticals and personal care products as molecular markers for raw wastewater contamination in surface and groundwater. Environ Sci Pollut Res 21:4727–4740

    Article  CAS  Google Scholar 

  • Vrana B, Klucarova V, Benicka E, Abou-Mrad N, Amdany R, Horakova S, Draxler A, Humer F, Gans O (2014) Passive sampling: an effective method for monitoring seasonal and spatial variability of dissolved hydrophobic organic contaminants and metals in Danube river. Environ Pollut 184:101–112

    Article  CAS  Google Scholar 

  • Vryzas Z, Vassiliou G, Alexoudis C, Papadopoulou-Mourkidou E (2009) Spatial and temporal distribution of pesticide residues in surface waters in northeastern Greece. Water Res 43:1–10

    Article  CAS  Google Scholar 

  • Vryzas Z, Alexoudis C, Vassiliou G, Galanis K, Papadopoulou-Mourkidou E (2011) Determination and aquatic risk assessment of pesticide residues in riparian drainage canals in northeastern Greece. Ecotoxicol Environ Saf 74:174–181

    Article  CAS  Google Scholar 

  • Xue N, Xu X, Jin Z (2005) Screening 31 endocrine-disrupting pesticides in water and surface sediment samples from Beijing Guanting reservoir. Chemosphere 61:1594–1606

    Article  CAS  Google Scholar 

  • Yang Y, Yun X, Liu M, Jiang Y, Li Q, Wang J (2014) Concentrations, distributions, sources, and risk assessment of organochlorine pesticides in surface water of the East Lake, China. Environ Sci Pollut Res 21:3041–3050

    Article  CAS  Google Scholar 

  • Young TA, Heidler J, Matos-Pérez CR, Sapkota A, Toler T, Gibson KE, Schwab KJ, Halden RU (2008) An ignition and in situ comparison of caffeine, triclosan, and triclocarban as indicators of sewage-derived microbes in surface waters. Environ Sci Technol 42:3335–3340

    Article  CAS  Google Scholar 

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Correspondence to Dimitra Voutsa.

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Terzopoulou, E., Voutsa, D. & Kaklamanos, G. A multi-residue method for determination of 70 organic micropollutants in surface waters by solid-phase extraction followed by gas chromatography coupled to tandem mass spectrometry. Environ Sci Pollut Res 22, 1095–1112 (2015). https://doi.org/10.1007/s11356-014-3397-3

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