Abstract
Three sampling campaigns were performed in the Lis River (Leiria, Portugal) in February of 2018, November of 2018, and May of 2019. River water and wastewater (influent and effluent) samples of two wastewater treatment plants were target of the study. A total of 25 samples were collected and 50 pesticides were monitored, including organochlorines, triazines, pyrethroids, and organophosphorus, among others. Most of the detected pesticides were insecticides and mainly organochlorines. Concentrations between 1.29 and 2134 ng/L were found. Aldrin, γ-HCH, and cypermethrin were detected in some samples in μg/L, being γ-HCH the pesticide most frequently detected with concentration in μg/L level. The pesticides with the highest detection frequency were (i) cypermethrin, HCB, methoxychlor, and ζ-HCH in river waters; (ii) isoproturon, cypermethrin, methoxychlor, pyrimethanil, γ-HCH, dieldrin, diuron, α-HCH, and α-endosulfan in effluents; and (iii) diuron and isoproturon in influents. The detection of the organochlorides and their degradation products is a consequence of their persistence in the environment, as their usage has long been prohibited in the European Union. Pesticides were grouped by their types in herbicides, insecticides, or fungicides and the detection and concentration for each type were discussed with the climatic conditions. Pesticide toxicity index was determined in the samples collected in the river.
Graphical abstract
This is a preview of subscription content, log in via an institution to check access.
Similar content being viewed by others
Data availability
All data generated or analysed during this study are included in this published article [and its supplementary information files].
References
Abdolazim B, Nazari Z, Rabiee MH, Raeesi G, Oveisi MR, Sadeghi N, Jannat B (2013) The organochlorine pesticides residue levels in Karun river water. Jundishapur J Nat Pharm Prod 8:41–46. https://doi.org/10.5812/jjnpp.6783
Abrantes N, Pereira R, Gonçalves F (2010) Occurrence of pesticides in water, sediments, and fish tissues in a lake surrounded by agricultural lands: concerning risks to humans and ecological receptors. Water Air Soil Pollut 212:77–88. https://doi.org/10.1007/s11270-010-0323-2
Antonious GF, Byers ME (1997) Fate and movement of endosulfan under field conditions. Environ Toxicol Chem 16:644–649. https://doi.org/10.1002/etc.5620160407
ATSDR-Endosulfan (2015): Agency for Toxic Substances and Disease Registry. Toxicological profile for endosulfan. Chapter 6. Potential for Human Exposure. page 221-272. Available at: https://www.atsdr.cdc.gov/toxprofiles/tp41-c6.pdf (accessed 2 March 2020)
Bala K, Geueke B, Miska M, Rentsch D, Poiger T, Dadhwa lM, Lal R, Holliger C, Kohler H (2012) Enzymatic conversion of ε-hexachlorocyclohexane and a heptachlorocyclohexane isomer, two neglected components of technical hexachlorocyclohexane. Environ Sci Technol 46:4051–4058. https://doi.org/10.1021/es204143x
Barceló D, Hennion MC (1997): Techniques and instrumentation in analytical chemistry. trace determination of pesticides and their degradation products in water, 19. Elsevier Science B.V, Amsterdam, The Netherlands. Hardcover ISBN: 9780444818423, eBook ISBN: 9780080543123
Barrie LA, Gregor D, Hargrave B, Lake R, Muir D, Shearer R, Tracey B, Bidleman T (1992) Arctic contaminants: sources, occurrence and pathways. Sci Total Environ 122:1–74. https://doi.org/10.1016/0048-9697(92)90245-N
Battaglin W, Fairchild J (2002) Potential toxicity of pesticides measured in midwestern streams to aquatic organisms. Water Sci Technol 45:95–102. https://doi.org/10.2166/wst.2002.0213
Cerrillo I, Granada A, López-Espinosa M-J, Olmos B, Jiménez M, Caño A, Olea N, Fátima Olea-Serrano M (2005) Endosulfan and its metabolites in fertile women, placenta, cord blood, and human milk. Environ Res 98:233–239. https://doi.org/10.1016/j.envres.2004.08.008
Covert SA, Shoda ME, Stackpoole SM, Stone WW (2020) Pesticide mixtures show potential toxicity to aquatic life in U.S. streams, water years 2013–2017. Sci Total Environ 745:141285. https://doi.org/10.1016/j.scitotenv.2020.141285
Cruzeiro C, Pardal MÂ, Rocha E, Rocha MJ (2015) Occurrence and seasonal loads of pesticides in surface water and suspended particulate matter from a wetland of worldwide interest—the Ria Formosa Lagoon, Portugal. Environ Monit Assess 187:669. https://doi.org/10.1007/s10661-015-4824-8
Cruzeiro C, Rocha E, Pardal MÂ, Rocha MJ (2016) Environmental assessment of pesticides in the Mondego River Estuary (Portugal). Mar Pollut Bull 103:240–246. https://doi.org/10.1016/j.marpolbul.2015.12.013
Cui S, Hough R, Yates K, Osprey M, Kerr C, Cooper P, Coull M, Zhang Z (2020) Effects of season and sediment-water exchange processes on the partitioning of pesticides in the catchment environment: implications for pesticides monitoring. Sci Total Environ 698:134228. https://doi.org/10.1016/j.scitotenv.2019.134228
Cumming H, Rücker C (2017) Octanol−water partition coefficient measurement by a simple 1HNMR method. ACS Omega 2:6244–6249. https://doi.org/10.1021/acsomega.7b01102
DL (1977) Decree Law. Decreto-Lei n° 152/97 de de 19 de Junho do Ministério do Ambiente e do Ordenamento do Território. DIÁRIO DA REPÚBLICA — I SÉRIE-A - N°139 — 19-6-1997, 2959-2968. Available at: https://dre.pt/application/conteudo/365343, Accessed date: 01 February 2021.
DL (2015): Decree Law. Decreto- Lei n° 218/2015 de 7 de outubro do Ministério do Ambiente e do Ordenamento do Território. Diário Da República, 1a Série-N° 196, 196, 8667–8685. Available at: https://dre.pt/application/file/a/70476114, Accessed date: 09 February 2020
Drożdżyński D (2008) Studies on residues of pesticides used in rape plants protection in surface waters of intensively exploited arable lands in Wielkopolska province of Poland. Ann Agric Environ Med 15:231–235
EC (1998): COUNCIL DIRECTIVE 98/83/EC of 3 November 1998 on the quality of water intended for human consumption. L 330. Available at: https://eur-lex.europa.eu/legal-content/EN/TXT/PDF/?uri=CELEX:31998L0083&from=EN, Accessed date: 04 February 2020), Official Journal of the European Communitie, pp. 32-54
EC (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: https://eur-lex.europa.eu/legal-content/EN/TXT/?uri=celex:32000L0060, Accessed date: 04 February 2020, Official Journal of the European Union, pp. 1-72
EC (2002): 2002/657/EC: Commission Decision of 12 August 2002 implementing Council Directive 96/23/EC concerning the performance of analytical methods and the interpretation of results.2002/657/EC. Available at: https://op.europa.eu/en/publication-detail/-/publication/ed928116-a955-4a84-b10a-cf7a82bad858/language-en, Accessed date: 14 April 2020. In: European Commission (Hrsg.), pp. 8-36
EC (2013): 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. Available at: https://eur-lex.europa.eu/LexUriServ/LexUriServ.do?uri=OJ:L:2013:226:0001:0017:EN:PDF, Accessed date: 04 February 2020, Official Journal of the European Union, pp. 1-17
FAO (2020) APPENDIX 3-Fact sheets on pesticides. Available: http://www.fao.org/3/X2570E/X2570E07.htm, Accessed date: 11 April 2020
Ferencz L, Balog A (2010) A pesticide survey in soil, water and foodstuffs from Central Romania. Carpath J Earth Env 5:111–118 http://www.cjees.ro/viewTopic.php?topicId=80~. Corpus ID: 32012314
Fernandes VC, Domingues VF, Mateus N, Delerue-Matos C (2011) Organochlorine pesticide residues in strawberries from integrated pest management and organic farming. J Agric Food Chem 59:7582–7591. https://doi.org/10.1021/jf103899r
Fujioka K, Casida JE (2007) Glutathione S-transferase conjugation of organophosphorus pesticides yields S-Phospho-, S-Aryl-, and S-alkylglutathione derivatives. Chem Res Toxicol 20:1211–1217. https://doi.org/10.1021/tx700133c
Fytiano K, Pitarakis K, Bobola E (2007) Monitoring of N-methylcarbamate pesticides in the Pinios River (central Greece) by HPLC. Int J Environ Anal Chem 86:131–145. https://doi.org/10.1080/03067310500248171
Gros M, Rodríguez-Mozaz S, Barceló D (2012) Fast and comprehensive multi-residue analysis of a broad range of human and veterinary pharmaceuticals and some of their metabolites in surface and treated waters by ultra-high-performance liquid chromatography coupled to quadrupole-linear ion trap tandem mass spectrometry. J Chromatogr A 1248:104–121. https://doi.org/10.1016/j.chroma.2012.05.084
Guillossou R, Le Roux J, Mailler R, Vulliet E, Morlay C, Nauleau F, Gasperi J, Rocher V (2019) Organic micropollutants in a large wastewater treatment plant: what are the benefits of an advanced treatment by activated carbon adsorption in comparison to conventional treatment? Chemosphere 218:1050–1060. https://doi.org/10.1016/j.chemosphere.2018.11.182
Hoffman DJ, Rattner BA, Burton Jr GA, Cairns Jr J (2003): eds. Handbook of ecotoxicology (2nd ed.). Boca Raton: Lewis Publishers. ISBN 1-56670-546-0. OCLC 49952447
IPMA (2020) Instituto Português do Mar e da Atmosfera (Portuguese Institute of the Sea and the Atmosphere). Available at: https://www.ipma.pt/pt/, Accessed date: 10 April 2020
Jelic A, Gros M, Ginebreda A, Cespedes-Sánchez R, Ventura F, Petrovic M, Barcelo D (2011) Occurrence, partition and removal of pharmaceuticals in sewage water and sludge during wastewater treatment. Water Res 45:1165–1176. https://doi.org/10.1016/j.watres.2010.11.010
Köck-Schulmeyer M, Villagrasa M, López de Alda M, Céspedes-Sánchez R, Ventura F, Barceló D (2013) Occurrence and behavior of pesticides in wastewater treatment plants and their environmental impact. Sci Total Environ 458-460:466–476. https://doi.org/10.1016/j.scitotenv.2013.04.010
Le TDH, Scharmüller A, Kattwinkel M, Kühne R, Schüürmann G, Schäfer RB (2017) Contribution of waste water treatment plants to pesticide toxicity in agriculture catchments. Ecotoxicol Environ Saf 145:135–141. https://doi.org/10.1016/j.ecoenv.2017.07.027
Leonard AW, Hyne RV, Lim RP, Leigh KA, Le J, Beckett R (2001) Fate and toxicity of endosulfan in Namoi River water and bottom sediment. J Environ Qual 30:750–759. https://doi.org/10.2134/jeq2001.303750x
Linden J (2013): Insect control on pig farms. Available at: https://thepigsite.com/articles/insect-control-on-pig-farms, Acessed date: 12 March 2020
Lockhart WL, Wagemann R, Tracey B, Sutherland D, Thomas DJ (1992) Presence and implications of chemical contaminants in the fresh waters of the Canadian Arctic. Sci Total Environ 122:165–245. https://doi.org/10.1016/0048-9697(92)90248-Q
Mansilha C, Melo A, Ferreira IMPLVO, Pinho O, Domingues V, Pinho C, Gameiro P (2011) Groundwater from infiltration galleries used for small public water supply systems: contamination with pesticides and endocrine disruptors. Bull Environ Contam Toxicol 87:312–318. https://doi.org/10.1007/s00128-011-0337-5
Margot J, Rossi L, Barry DA, Holliger C (2015) A review of the fate of micropollutants in wastewater treatment plants. Wiley Interdiscip Rev Water 2:457–487. https://doi.org/10.1002/wat2.1090
Masiá A, Campo J, Vázquez-Roig P, Blasco C, Picó Y (2013) Screening of currently used pesticides in water, sediments and biota of the Guadalquivir River Basin (Spain). J Hazard Mater 263:95–104. https://doi.org/10.1016/j.jhazmat.2013.09.035
Mekonnen TF, Panne U, Koch M (2019) Glucosylation and glutathione conjugation of chlorpyrifos and fluopyram metabolites using electrochemistry/mass spectrometry. Molecules 24:898. https://doi.org/10.3390/molecules24050898
Münze R, Hannemann C, Orlinskiy P, Gunold R, Paschke A, Foit K, Becker J, Kaske O, Paulsson E, Peterson M, Jernstedt H, Kreuger J, Schüürmann G, Liess M (2017) Pesticides from wastewater treatment plant effluents affect invertebrate communities. Sci Total Environ 599-600:387–399. https://doi.org/10.1016/j.scitotenv.2017.03.008
NATA (2013): Guidelines for the validation and verification of quantitative and qualitative test methods. Technical Note 17. National Association of Testing Authorities, Australia. Available at: https://www.nata.com.au/phocadownload/gen-accreditation-guidance/Validation-and-Verification-of-Quantitative-and-Qualitative-Test-Methods.pdf, acessed 01 January 2021
Nowell LH, Norman JE, Moran PW, Martin JD, Stone WW (2014) Pesticide Toxicity Index—a tool for assessing potential toxicity of pesticide mixtures to freshwater aquatic organisms. Sci Total Environ 476–477:144–157. https://doi.org/10.1016/j.scitotenv.2013.12.088
Paíga P, Santos LHMLM, Ramos S, Jorge S, Silva JG, Delerue-Matos C (2016) Presence of pharmaceuticals in the Lis river (Portugal): sources, fate and seasonal variation. Sci Total Environ 573:164–177. https://doi.org/10.1016/j.scitotenv.2016.08.089
Paíga P, Santos LHMLM, Delerue-Matos C (2017) Development of a multi-residue method for the determination of human and veterinary pharmaceuticals and some of their metabolites in aqueous environmental matrices by SPE-UHPLC–MS/MS. J Pharm Biomed Anal 135:75–86. https://doi.org/10.1016/j.jpba.2016.12.013
Paíga P, Correia M, Fernandes MJ, Silva A, Carvalho M, Vieira J, Jorge S, Silva JG, Freire C, Delerue-Matos C (2019) Assessment of 83 pharmaceuticals in WWTP influent and effluent samples by UHPLC-MS/MS: hourly variation. Sci Total Environ 648:582–600. https://doi.org/10.1016/j.scitotenv.2018.08.129
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. https://doi.org/10.1016/j.scitotenv.2014.04.088
Pitarch E, Medina C, Portolés T, López FJ, Hernández F (2007) Determination of priority organic micro-pollutants in water by gas chromatography coupled to triple quadrupole mass spectrometry. Anal Chim Acta 583:246–258. https://doi.org/10.1016/j.aca.2006.10.012
Ramesh A, Tanabe S, Iwata H, Tatsukawa R, Subramanian AN, Mohan D, Venugopalan VK (1990) Seasonal variation of persistent organochlorine insecticide residues in Vellar River waters in Tamil Nadu, South India. Environ Pollut 67:289–304. https://doi.org/10.1016/0269-7491(90)90067-M
Rao DMR, Murty AS (1980) Persistence of endosulfan in soils. J Agric Food Chem 28:1099–1101. https://doi.org/10.1021/jf60232a012
Rashid SS, Liu Y-Q (2020) Assessing environmental impacts of large centralized wastewater treatment plants with combined or separate sewer systems in dry/wet seasons by using LCA. Environ Sci Pollut Res 27:15674–15690. https://doi.org/10.1007/s11356-020-08038-2
Reungoat J, Macova M, Escher BI, Carswell S, Mueller JF, Keller J (2010) Removal of micropollutants and reduction of biological activity in a full scale reclamation plant using ozonation and activated carbon filtration. Water Res 44:625–637. https://doi.org/10.1016/j.watres.2009.09.048
Ritter L, Solomon KR, Forget J, Stemeroff M, O’Leary C (1995) A review of selected persistent organic pollutants: DDT, Aldrin, Dieldrin, Endrin, Chlordane, Heptachlor, Hexachlorobenzene, Mïrex, Toxaphene, Polychlorinated biphenyls, Dioxins, and Furans. PCS/95.39. A formal publication of the World Health Organization (WHO). Available at: https://www.who.int/ipcs/assessment/en/pcs953920040513.pdf, Acessed date: 01 February 2020.1-62.
Sánchez-González S, Pose-Juan E, Herrero-Hernández E, Álvarez-Martín A, Sánchez-Martín MJ, Rodríguez-Cruz S (2013) Pesticide residues in groundwaters and soils of agricultural areas in the Águeda River Basin from Spain and Portugal. Int J Environ Anal Chem 93:1585–1601. https://doi.org/10.1080/03067319.2013.814122
Şengül Ü (2016) Comparing determination methods of detection and quantification limits for aflatoxin analysis in hazelnut. J Food Drug Anal 24:56–62. https://doi.org/10.1016/j.jfda.2015.04.009
Singh SN (2016) Microbe-induced degradation of pesticides. Springer International Publishing.107. https://doi.org/10.1007/978-3-319-45156-5
Soares AFS, Leão MMD, de Faria VHF, da Costa MCM, Moura ACM, Ramos VDV, Neto MRV, da Cost aP (2013) Occurrence of pesticides from coffee crops in surface water. Ambi-Agua 8: 62-72. https://doi.org/10.4136/ambi-agua.1053
Spahr S, Teixidó M, Sedlak DL, Luthy RG (2020) Hydrophilic trace organic contaminants in urban stormwater: occurrence, toxicological relevance, and the need to enhance green stormwater infrastructure. Environ Sci-Wat Res 6:15–44. https://doi.org/10.1039/C9EW00674E
Stamatis N, Hela D, Konstantinou I (2010) Pesticide inputs from the sewage treatment plant of Agrinio to River Acheloos, western Greece: occurrence and removal. Water Sci Technol 62(5):1098–1105. https://doi.org/10.2166/wst.2010.932
Stenerson KK, Buchanan MD, Prevent GC (2020) Inlet Problems BEFORE They Cost You Time and Money. Reporter US, Volume 27.3. Available at: https://www.sigmaaldrich.com/technical-documents/articles/reporter-us/gc-inlet-problem-prevention.html, Acessed date: 14 April 2020, Reporter US
Thomas DJ, Tracey B, Marshall H, Norstrom RJ (1992) Arctic terrestrial ecosystem contamination. Sci Total Environ 122:135–164. https://doi.org/10.1016/0048-9697(92)90247-P
USEPA (2012): US Environmental Protection Agency. Ecological Structure Activity Relationships (ECOSAR) Predictive Model v1.11, Available at: https://goo.gl/xBM2VN
Wheeler W (2002): Pesticides in Agriculture and the Environment. 1st Edition. . CRC Press, New York, USA. ISBN-10 : 0824708091, ISBN-13 : 978-0824708092
Zhang P, Song JM, Yuan HM (2009) Persistent organic pollutants residues in the sediments and mollusks from the Bohai Sea coastal areas, North China: an overview. Environ Int 35:632–646. https://doi.org/10.1016/j.envint.2008.09.014
Zhou Y, Meng J, Zhang M, Chen S, He B, Zhao H, Li Q, Zhang S, Wang T (2019) Which type of pollutants need to be controlled with priority in wastewater treatment plants: traditional or emerging pollutants? Environ Int 131:104982. https://doi.org/10.1016/j.envint.2019.104982
Acknowledgements
The authors are grateful for the financial support from the Fundação para a Ciência e a Tecnologia (FCT) / Ministério da Ciência, Tecnologia e Ensino Superior (MCTES) through national funds (Portugal) (UIDB/50006/2020). The authors would like to thank the EU and FCT / UEFISCDI /FORMAS for funding in the frame of the collaborative international consortium REWATER financed under the ERA-NET Cofund WaterWorks2015 Call. This ERA-NET is an integral part of the 2016 Joint Activities developed by the Water Challenges for a Changing World Joint Programme Initiative (WaterJPI/0007/2016). The authors would like to also thank the financial support from the project PTDC/ASP-PES/29547/2017–CECs(Bio)Sensing-(Bio)sensors for assessment of contaminants of emerging concern in fishery commodities, by national funds by FCT / MCTES and co-supported by Fundo Europeu de Desenvolvimento Regional (FEDER) throughout POC - Programa Operacional Competitividade e Internacionalização. S. Sousa is grateful to FCT for the Ph.D grant (SFRH/BD/137516/2018) and Luciana Bitencourt is grateful for the financial support from the Instituto Federal de Educação, Ciências e Tecnologia de Sergipe.
Funding
This study received funding from Fundação para a Ciência e a Tecnologia (FCT) / Ministério da Ciência, Tecnologia e Ensino Superior (MCTES) through national funds (Portugal) (UIDB/50006/2020); EU and FCT / UEFISCDI /FORMAS for funding in the frame of the collaborative international consortium REWATER financed under the ERA-NET Cofund WaterWorks2015 Call (WaterJPI/0007/2016); FCT / MCTES and co-supported by Fundo Europeu de Desenvolvimento Regional (FEDER) throughout POC - Programa Operacional Competitividade e Internacionalização: PTDC/ASP-PES/29547/2017; Ph.D grant (SFRH/BD/137516/2018).
Author information
Authors and Affiliations
Contributions
Paula Paíga: Conceptualization; Methodology, Validation and Data Curation for the pesticides analysed by liquid chromatography; Investigation, Formal analysis; Writing - Original Draft.
Sara Sousa: Methodology, Validation and Data Curation for the pesticides analysed in gas chromatography, Investigation, Writing - Review & Editing.
José Vera: Methodology, Validation and Data Curation for the pesticides analysed in gas chromatography; Investigation.
Luciana Bitencourt: Methodology, Validation, and Data Curation for the pesticides analysed in liquid chromatography, Investigation.
Joana Vieira: Conceptualization, Resources.
Sandra Jorge: Conceptualization, Resources.
Jaime Gabriel Silva: Conceptualization, Resources.
Manuela Correia: Conceptualization, Supervision, Writing - Review & Editing.
Valentina F. Domingues: Conceptualization, Supervision, Writing - Review & Editing.
Cristina Delerue-Matos: Conceptualization, Supervision, Project administration, Funding acquisition, Writing - Review & Editing.
Corresponding author
Ethics declarations
Ethics approval and consent to participate
Not applicable.
Consent for publication
Not applicable.
Competing interests
The authors declare no competing interests.
Additional information
Responsible Editor: Ester Heath
Publisher’s note
Springer Nature remains neutral with regard to jurisdictional claims in published maps and institutional affiliations.
Highlights
• The total pesticides concentration increased from the river source to the mouth.
• Organochlorine group and insecticide type were the most detected pesticides.
• Levels of μg/L were found for γ-HCH and aldrin in river and α-and γ-HCH and cypermethrin in effluent samples.
• The highest detection frequency found in influent was 50%, in river 67%, and in effluent 100%.
• The concentration of chlorpyrifos, cypermethrin, and HCH pesticides exceeds the environmental quality standards.
Supplementary Information
ESM 1
(DOC 2021 kb)
Rights and permissions
About this article
Cite this article
Paíga, P., Sousa, S., Vera, J. et al. Multi-residue analysis of fifty pesticides in river waters and in wastewaters. Environ Sci Pollut Res 28, 66787–66803 (2021). https://doi.org/10.1007/s11356-021-15134-4
Received:
Accepted:
Published:
Issue Date:
DOI: https://doi.org/10.1007/s11356-021-15134-4