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Determination of 18 Biocides in Both the Dissolved and Particulate Fractions of Urban and Surface Waters by HPLC-MS/MS

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Abstract

A robust method is provided to analyze 18 hydrophilic and hydrophobic biocides in both dissolved and particulate fractions of five types of urban and surface waters using high-performance liquid chromatography coupled to tandem mass spectrometry. The linearity, accuracy, and intermediate precision were validated. The target biocides were enriched by solid-phase extraction using Chromabond HR-X 200-mg cartridges and eluted with methanol, ethyl acetate, and dichloromethane. Suspended matter was extracted by microwave-assisted extraction in methanol and dichloromethane. Recoveries and variability (respectively > 75% and < 30% for most of the target biocides and matrices) made it possible to quantify biocides at a trace level in all matrices. Limits of quantification were in the range of nanograms per liter in the dissolved fraction and in the range of nanograms per gram of dry weight in the particulate fraction for most of the biocides and matrices, and were generally lower than those reported in previous studies. The method was successfully applied to surface waters, treated and untreated wastewater, combined sewer overflows, and stormwater, providing unique data in these matrices for some substances, in particular with respect to particle contamination. In urban waters, concentrations of most of the biocides ranged from 10 to 200 ng/L. Diuron, isothiazolinone, and benzalkonium concentrations could reach 0.9, 0.9, and 20 μg/L respectively. In rivers, most of the biocides were measured at less than 10 ng/L, but higher concentrations were observed for benzalkoniums (up to 200 ng/L) or after rain events, which indicates biocide transfer from urban surfaces into the aquatic environment during wet weather.

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References

  • Andrade, T. S., Henriques, J. F., Almeida, A. R., Machado, A. L., Koba, O., Giang, P. T., Soares, A. M. V. M., & Domingues, I. (2016). Carbendazim exposure induces developmental, biochemical and behavioural disturbance in zebrafish embryos. Aquatic Toxicology, 170, 390–399. https://doi.org/10.1016/j.aquatox.2015.11.017.

    Article  CAS  Google Scholar 

  • Bester, K., & Lamani, X. (2010). Determination of biocides as well as some biocide metabolites from facade run-off waters by solid phase extraction and high performance liquid chromatographic separation and tandem mass spectrometry detection. Journal of Chromatography A, 1217(32), 5204–5214. https://doi.org/10.1016/j.chroma.2010.06.020.

    Article  CAS  Google Scholar 

  • Bester, K., Scholes, L., Wahlberg, C., & McArdell, C. S. (2008). Sources and mass flows of xenobiotics in urban water cycles—an overview on current knowledge and data gaps. Water, Air, and Soil Pollution, 17.

  • Birch, H., Mikkelsen, P. S., Jensen, J. K., & Lützhøft, H.-C. H. (2011). Micropollutants in stormwater runoff and combined sewer overflow in the Copenhagen area, Denmark. Water Science & Technology, 64(2), 485–493. https://doi.org/10.2166/wst.2011.687.

    Article  CAS  Google Scholar 

  • Bollmann, U. E., Vollertsen, J., Carmeliet, J., & Bester, K. (2014b). Dynamics of biocide emissions from buildings in a suburban stormwater catchment – concentrations, mass loads and emission processes. Water Research, 56, 66–76. https://doi.org/10.1016/j.watres.2014.02.033.

    Article  CAS  Google Scholar 

  • Bollmann, U. E., Tang, C., Eriksson, E., Jönsson, K., Vollertsen, J., & Bester, K. (2014a). Biocides in urban wastewater treatment plant influent at dry and wet weather: concentrations, mass flows and possible sources. Water Research, 60, 64–74. https://doi.org/10.1016/j.watres.2014.04.014.

    Article  CAS  Google Scholar 

  • Bollmann, U. E., Minelgaite, G., Schlüsener, M., Ternes, T., Vollertsen, J., & Bester, K. (2016). Leaching of terbutryn and its photodegradation products from artificial walls under natural weather conditions. Environmental Science & Technology, 50(8), 4289–4295. https://doi.org/10.1021/acs.est.5b05825.

    Article  CAS  Google Scholar 

  • Bollmann, U. E., Minelgaite, G., Schlüsener, M., Ternes, T. A., Vollertsen, J., & Bester, K. (2017). Photodegradation of octylisothiazolinone and semi-field emissions from facade coatings. Scientific Reports, 7, 41501-1–9. https://doi.org/10.1038/srep41501.

  • Bressy, A., Gromaire, M.-C., Lorgeoux, C., Saad, M., Leroy, F., & Chebbo, G. (2012). Towards the determination of an optimal scale for stormwater quality management: micropollutants in a small residential catchment. Water Research, 46(20), 6799–6810. https://doi.org/10.1016/j.watres.2011.12.017.

    Article  CAS  Google Scholar 

  • Burkhardt, M., Junghans, M., Zuleeg, S., Boller, M., Schoknecht, U., Lamani, X., Bester, K., Vonbank, R., & Simmler, S. (2009). Biozide in Gebäudefassaden – ökotoxikologische Effekte, Auswaschung und Belastungsabschätzung für Gewässer. Umweltwissenschaften und Schadstoff-Forschung, 21(1), 36–47. https://doi.org/10.1007/s12302-008-0033-1.

    Article  CAS  Google Scholar 

  • Burkhardt, M., Zuleeg, S., Vonbank, R., Schmid, P., Hean, S., Lamani, X., et al. (2011). Leaching of additives from construction materials to urban storm water runoff. Water Science & Technology, 63(9), 1974–1982. https://doi.org/10.2166/wst.2011.128.

    Article  CAS  Google Scholar 

  • Burkhardt, M., Zuleeg, S., Vonbank, R., Bester, K., Carmeliet, J., Boller, M., & Wangler, T. (2012). Leaching of biocides from Façades under natural weather conditions. Environmental Science & Technology, 46(10), 5497–5503. https://doi.org/10.1021/es2040009.

    Article  CAS  Google Scholar 

  • Chen, Z.-F., Ying, G.-G., Lai, H.-J., Chen, F., Su, H.-C., Liu, Y.-S., et al. (2012). Determination of biocides in different environmental matrices by use of ultra-high-performance liquid chromatography–tandem mass spectrometry. Analytical and Bioanalytical Chemistry, 404(10), 3175–3188. https://doi.org/10.1007/s00216-012-6444-2.

    Article  CAS  Google Scholar 

  • Chitescu, C. L., Oosterink, E., de Jong, J., & Stolker, A. A. M. L. (2012). Ultrasonic or accelerated solvent extraction followed by U-HPLC-high mass accuracy MS for screening of pharmaceuticals and fungicides in soil and plant samples. Talanta, 88, 653–662.

    Article  CAS  Google Scholar 

  • Cotton, J., Leroux, F., Broudin, S., Poirel, M., Corman, B., Junot, C., & Ducruix, C. (2016). Development and validation of a multiresidue method for the analysis of more than 500 pesticides and drugs in water based on on-line and liquid chromatography coupled to high resolution mass spectrometry. Water Research, 104, 20–27. https://doi.org/10.1016/j.watres.2016.07.075.

    Article  CAS  Google Scholar 

  • Dulio, V., von der Ohe, P. C., Botta, F., Ipolyi, I., Ruedel, H., & Slobodnik, J. (2015). The NORMAN network - special view on biocides as emerging substances, présentation workshop NORMAN, 25–26 juin 2015, Berlin, Allemagne. Berlin. http://www.norman-network.net/?q=node/230

  • Friedle, A., Thumulla, J., & Snepvangers, K. (2008). Quaternary ammonium compounds (QUAT) in house dust. Indoor Air, 4, 17–22.

    Google Scholar 

  • Gasperi, J., Garnaud, S., Rocher, V., & Moilleron, R. (2008). Priority pollutants in wastewater and combined sewer overflow. Science of the Total Environment, 407(1), 263–272. https://doi.org/10.1016/j.scitotenv.2008.08.015.

    Article  CAS  Google Scholar 

  • Gasperi, J., Sebastian, C., Ruban, V., Delamain, M., Percot, S., Wiest, L., et al. (2013). Micropollutants in urban stormwater: occurrence, concentrations, and atmospheric contributions for a wide range of contaminants in three French catchments. Environmental Science and Pollution Research, 21(8), 5267–5281. https://doi.org/10.1007/s11356-013-2396-0.

    Article  CAS  Google Scholar 

  • Geara-Matta, D. (2012). Flux et sources des parabènes, du triclosan et du triclocarban en milieux urbains denses: comparaison entre Paris et Beyrouth. In Thèse de doctorat (Sciences de l’Univers et Environnement) (178 p). Paris-Est: Université.

    Google Scholar 

  • Geissen, V., Mol, H., Klumpp, E., Umlauf, G., Nadal, M., van der Ploeg, M., et al. (2015). Emerging pollutants in the environment: a challenge for water resource management. International Soil and Water Conservation Research, 3(1), 57–65. https://doi.org/10.1016/j.iswcr.2015.03.002.

    Article  Google Scholar 

  • Hepperle, J., Schüle, E., Kolberg, D., & Scherbaum, E. (2002). Determination of quaternary ammonium compound residues in fruits and vegetables by QuEChERS following LC-MS/MS analysis. 5 p. https://pdfs.semanticscholar.org/9f07/d9f1ae9b695391792d05fb5027df23225585.pdf

  • Hildebrandt, A., Lacorte, S., & Barceló, D. (2007). Assessment of priority pesticides, degradation products, and pesticide adjuvants in groundwaters and top soils from agricultural areas of the Ebro river basin. Analytical and Bioanalytical Chemistry, 387, 1459–1468.

    Article  CAS  Google Scholar 

  • Huang, O., Zhang, J., Xiong, S., Peng, X., Wei, G., Liu, L., et al. (2018). Development of ultrasound-assisted extraction of commonly used azole antifungals in soils. Analytical Methods, 10(44), 5265–5272.

    Article  CAS  Google Scholar 

  • Jiang, J., Wu, S., Wang, Y., An, X., Cai, L., Zhao, X., & Wu, C. (2015). Carbendazim has the potential to induce oxidative stress, apoptosis, immunotoxicity and endocrine disruption during zebrafish larvae development. Toxicology In Vitro, 29(7), 1473–1481. https://doi.org/10.1016/j.tiv.2015.06.003.

    Article  CAS  Google Scholar 

  • Juksu, K., Zhao, J.-L., Liu, Y.-S., Yao, L., Sarin, C., Sreesai, S., et al. (2019). Occurrence, fate and risk assessment of biocides in wastewater treatment plants and aquatic environments in Thailand. Science of the Total Environment, 690, 1110–1119.

    Article  CAS  Google Scholar 

  • Kalogridi, E.-C., Christophoridis, C., Bizani, E., Drimaropoulou, G., & Fytianos, K. (2014). Part II: Temporal and spatial distribution of multiclass pesticide residues in lake sediments of northern Greece: application of an optimized MAE-LC-MS/MS pretreatment and analytical method. Environmental Science and Pollution Research, 21(12), 7252–7262.

    Article  CAS  Google Scholar 

  • Launay, M. A., Dittmer, U., & Steinmetz, H. (2016). Organic micropollutants discharged by combined sewer overflows – characterisation of pollutant sources and stormwater-related processes. Water Research, 104, 82–92. https://doi.org/10.1016/j.watres.2016.07.068.

    Article  CAS  Google Scholar 

  • Masiá, A., Vásquez, K., Campo, J., & Picó, Y. (2015). Assessment of two extraction methods to determine pesticides in soils, sediments and sludges. Application to the Túria River Basin. Journal of Chromatography A, 1378, 19–31. https://doi.org/10.1016/j.chroma.2014.11.079.

    Article  CAS  Google Scholar 

  • Merel, S., Benzing, S., Gleiser, C., Di Napoli-Davis, G., & Zwiener, C. (2018). Occurrence and overlooked sources of the biocide carbendazim in wastewater and surface water. Environmental Pollution, 239, 512–521. https://doi.org/10.1016/j.envpol.2018.04.040.

    Article  CAS  Google Scholar 

  • Miege, C., Dugay, J., & Hennion, M. C. (2003). Optimization, validation and comparison of various extraction techniques for the trace determination of polycyclic aromatic hydrocarbons in sewage sludges by liquid chromatography coupled to diode-array and fluorescence detection. Journal of Chromatography A, 995(1–2), 87–97.

    Article  CAS  Google Scholar 

  • Mohr, S., Schröder, H., Feibicke, M., Berghahn, R., Arp, W., & Nicklisch, A. (2008). Long-term effects of the antifouling booster biocide Irgarol 1051 on periphyton, plankton and ecosystem function in freshwater pond mesocosms. Aquatic Toxicology, 90(2), 109–120. https://doi.org/10.1016/j.aquatox.2008.08.004.

    Article  CAS  Google Scholar 

  • Mompelat, S., Fourmond, M.-P., Laurentie, M., Verdon, E., Hurtaud-Pessel, D., & Abjean, J.-P. (2015). Validation of a liquid chromatography–high-resolution mass spectrometry method for the analysis of ceftiofur in poultry muscle, kidneys and plasma: a unique accuracy profile for each and every matrix. Journal of Chromatography A, 1407, 119–129. https://doi.org/10.1016/j.chroma.2015.06.043.

    Article  CAS  Google Scholar 

  • Moschet, C., Piazzoli, A., Singer, H., & Hollender, J. (2013). Alleviating the reference standard dilemma using systematic exact mass suspect screening approach with liquid chromatography-high resolution mass spectrometry. Analytical Chemistry, 85, 10312–10320.

    Article  CAS  Google Scholar 

  • Moschet, C., Wittmer, I., Simovic, J., Junghans, M., Piazzoli, A., Singer, H. P., et al. (2014). How a complete pesticide screening changes the assessment of surface water quality. Environmental Science & Technology, 48(10), 5423–5432. https://doi.org/10.1021/es500371t.

    Article  CAS  Google Scholar 

  • Östman, M., Lindberg, R. H., Fick, J., Björn, E., & Tysklind, M. (2017). Screening of biocides, metals and antibiotics in Swedish sewage sludge and wastewater. Water Research, 115, 318–328.

    Article  Google Scholar 

  • Paijens, C., Bressy, A., Frère, B., & Moilleron, R. (2019). Prioritization of leached biocides from building materials towards aquatic environment monitoring (in French), Techniques Sciences Méthodes, 12, 197–219. https://doi.org/10.36904/tsm/201912197.

  • Paijens, C., Bressy, A., Frère, B., & Moilleron, R. (2020). Biocide emissions from building materials during wet weather: identification of substances, mechanism of release and transfer to the aquatic environment. Environmental Science and Pollution Research, 27, 3768–3791. https://doi.org/10.1007/s11356-019-06608-7.

  • Potter, T. L., & Coffin, A. W. (2017). Assessing pesticide wet deposition risk within a small agricultural watershed in the Southeastern Coastal Plain (USA). Science of the Total Environment, 580, 158–167.

    Article  CAS  Google Scholar 

  • Rafoth, A., Gabriel, S., Sacher, F., & Brauch, H.-J. (2007). Analysis of isothiazolinones in environmental waters by gas chromatography–mass spectrometry. Journal of Chromatography A, 1164(1–2), 74–81. https://doi.org/10.1016/j.chroma.2007.07.040.

    Article  CAS  Google Scholar 

  • Sánchez-Rodríguez, A., Sosa-Ferrera, Z., & Santana-Rodríguez, J. J. (2011). Applicability of microwave-assisted extraction combined with LC–MS/MS in the evaluation of booster biocide levels in harbour sediments. Chemosphere, 82, 96–102.

    Article  Google Scholar 

  • Scheyer, A., Morville, S., Mirabel, P., & Millet, M. (2007). Pesticides analysed in rainwater in Alsace region (Eastern France): comparison between urban and rural sites. Atmospheric Environment, 41, 7241–7252.

    Article  CAS  Google Scholar 

  • Shah, J., Jan, M. R., Ara, B., & Shehzad, F.-N. (2011). Quantification of triazine herbicides in soil by microwave-assisted extraction and high-performance liquid chromatography. Environmental Monitoring and Assessment, 178(111–119).

  • Singer, H. P., Jaus, S., Hanke, I., Lück, A., Hollender, J., & Alder, A. C. (2010). Determination of biocides and pesticides by on-line solid phase extraction coupled with mass spectrometry and their behaviour in wastewater and surface water. Environmental Pollution, 158(10), 3054–3064. https://doi.org/10.1016/j.envpol.2010.06.013.

    Article  CAS  Google Scholar 

  • Slimani, K., Féret, A., Pirotais, Y., Maris, P., Abjean, J.-P., & Hurtaud-Pessel, D. (2017). Liquid chromatography-tandem mass spectrometry multiresidue method for the analysis of quaternary ammonium compounds in cheese and milk products: development and validation using the total error approach. Journal of Chromatography A, 1517, 86–96. https://doi.org/10.1016/j.chroma.2017.08.034.

    Article  CAS  Google Scholar 

  • Stipičević, S., Galzina, N., Udiković-Kolić, N., Jurina, T., Mendaš, G., Dvoršćak, M., et al. (2015). Distribution of terbuthylazine and atrazine residues in crop-cultivated soil: the effect of herbicide application rate on herbicide persistence. Geoderma, 259–260, 300–309.

    Article  Google Scholar 

  • Uhl, M., Gans, O., Grillitsch, B., Fürhacker, M., & Kreuzinger, N. (2005). Grundlagen Zur Risikoabschätzung Für Quaternäre Ammoniumverbindungen, 157 p. http://www.academia.edu/download/40282155/Grundlagen_zur_Risikoabschtzung_fr_quate20151122-11272-eisz97.pdf.

  • Van de Voorde, A., Lorgeoux, C., Gromaire, M.-C., & Chebbo, G. (2012). Analysis of quaternary ammonium compounds in urban stormwater samples. Environmental Pollution, 164, 150–157. https://doi.org/10.1016/j.envpol.2012.01.037.

    Article  CAS  Google Scholar 

  • Vermeirssen, E. L. M., Campiche, S., Dietschweiler, C., Werner, I., & Burkhardt, M. (2018). Ecotoxicological assessment of immersion samples from facade render containing free or encapsulated biocides: ecotoxicity of leachates from facade renders with biocides. Environmental Toxicology and Chemistry, 37(8), 2246–2256. https://doi.org/10.1002/etc.4176.

    Article  CAS  Google Scholar 

  • Vial, J., Le Mapihan, K., & Jardy, A. (2003). What is the best means of estimating the detection and quantification limits of a chromatographic method? Chromatographia, 57(1), S303–S306.

    Article  Google Scholar 

  • Wick, A., Fink, G., & Ternes, T. A. (2010). Comparison of electrospray ionization and atmospheric pressure chemical ionization for multi-residue analysis of biocides, UV-filters and benzothiazoles in aqueous matrices and activated sludge by liquid chromatography–tandem mass spectrometry. Journal of Chromatography A, 1217(14), 2088–2103. https://doi.org/10.1016/j.chroma.2010.01.079.

    Article  CAS  Google Scholar 

  • Wicke, D., Matzinger, A., & Rouault, P. (2015). Relevanz organischer Spurenstoffe im Regenwasserabfluss Berlins. Kompetenzzentrum Wasser Berlin, 99 p. https://www.kompetenz-wasser.de/wp-content/uploads/2017/11/abschlussbericht_ogre_final_rev2.pdf

  • Wieck, S., Olsson, O., & Kümmerer, K. (2016). Possible underestimations of risks for the environment due to unregulated emissions of biocides from households to wastewater. Environment International, 94, 695–705.

    Article  CAS  Google Scholar 

  • Wieck, S., Olsson, O., & Kümmerer, K. (2018). Not only biocidal products: washing and cleaning agents and personal care products can act as further sources of biocidal active substances in wastewater. Environment International, 115, 247–256. https://doi.org/10.1016/j.envint.2018.03.040.

    Article  CAS  Google Scholar 

  • Zgheib, S., Moilleron, R., & Chebbo, G. (2012). Priority pollutants in urban stormwater: part 1 – case of separate storm sewers. Water Research, 46(20), 6683–6692. https://doi.org/10.1016/j.watres.2011.12.012.

    Article  CAS  Google Scholar 

  • Zhang, H., Watts, S., Philix, M. C., Snyder, S. A., & Ong, C. N. (2018). Occurrence and distribution of pesticides in precipitation as revealed by targeted screening through GC-MS/MS. Chemosphere, 211, 210–217.

    Article  CAS  Google Scholar 

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Acknowledgments

The authors thank the Brigade Fluviale de la Préfecture de Police (Major Bizeray) and the Brigade Fluviale de la Gendarmerie Nationale des Yvelines (Major Duquesnois), the SIAAP (in particular Vincent Rocher, Romain Mailler, and Céline Briand), and the City of Paris (in particular Pascale Neveu and Frédéric Béthouart) for their assistance during sampling campaigns.

Funding

The authors gratefully acknowledge the Central Laboratory of the Police Prefecture of Paris (LCPP) for the funding of this work. The study has been performed within the framework of the OPUR research program funded by the Seine-Normandy Water Agency, the City of Paris, the greater Paris sanitation authority (SIAAP), the Hauts-de-Seine Departmental Council, the Seine Saint-Denis Departmental Council, and the Val-de-Marne Departmental Council.

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  1. Leesu, Ecole des Ponts, Univ Paris Est Creteil, Marne-la-Vallée, France

    Claudia Paijens, Emilie Caupos, Régis Moilleron & Adèle Bressy

  2. Laboratoire Central de la Préfecture de Police, Paris, France

    Claudia Paijens & Bertrand Frère

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  1. Claudia Paijens
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Paijens, C., Frère, B., Caupos, E. et al. Determination of 18 Biocides in Both the Dissolved and Particulate Fractions of Urban and Surface Waters by HPLC-MS/MS. Water Air Soil Pollut 231, 210 (2020). https://doi.org/10.1007/s11270-020-04546-6

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