Skip to main content

Advertisement

Log in

Risk assessment of herbicides and booster biocides along estuarine continuums in the Bay of Vilaine area (Brittany, France)

  • Ecotoxicology of estuaries in France and Québec, Canada
  • Published:
Environmental Science and Pollution Research Aims and scope Submit manuscript

Abstract

A 2-year study was implemented to characterize the contamination of estuarine continuums in the Bay of Vilaine area (NW Atlantic Coast, Southern Brittany, France) by 30 pesticide and biocide active substances and metabolites. Among these, 11 triazines (ametryn, atrazine, desethylatrazine, desethylterbuthylazine, desisopropyl atrazine, Irgarol 1051, prometryn, propazine, simazine, terbuthylazine, and terbutryn), 10 phenylureas (chlortoluron, diuron, 1-(3,4-dichlorophenyl)-3-methylurea, fenuron, isoproturon, 1-(4-isopropylphenyl)-3-methylurea, 1-(4-isopropylphenyl)-urea, linuron, metoxuron, and monuron), and 4 chloroacetanilides (acetochlor, alachlor, metolachlor, and metazachlor) were detected at least once. The objectives were to assess the corresponding risk for aquatic primary producers and to provide exposure information for connected studies on the responses of biological parameters in invertebrate sentinel species. The risk associated with contaminants was assessed using risk quotients based on the comparison of measured concentrations with original species sensitivity distribution-derived hazardous concentration values. For EU Water Framework Directive priority substances, results of monitoring were also compared with regulatory Environmental Quality Standards. The highest residue concentrations and risks for primary producers were recorded for diuron and Irgarol 1051 in Arzal reservoir, close to a marina. Diuron was present during almost the all survey periods, whereas Irgarol 1051 exhibited a clear seasonal pattern, with highest concentrations recorded in June and July. These results suggest that the use of antifouling biocides is responsible for a major part of the contamination of the lower part of the Vilaine River course for Irgarol 1051. For diuron, agricultural sources may also be involved. The presence of isoproturon and chloroacetanilide herbicides on some dates indicated a significant contribution of the use of plant protection products in agriculture to the contamination of Vilaine River. Concentration levels and associated risk were always lower in estuarine sites than in the reservoir, suggesting that Arzal dam reduces downstream transfer of contaminants and favors their degradation in the freshwater part of the estuary. Results of the additional monitoring of two tidal streams located downstream of Arzal dam suggested that, although some compounds may be transferred to the estuary, their impact was probably very low. Dilution by marine water associated with tidal current was also a major factor of concentration reduction. It is concluded that the highest risks associated to herbicides and booster biocides concerned the freshwater part of the estuary and that its brackish/saltwater part was exposed to a moderate risk, although some substances may sometimes exhibit high concentration but mainly at low tide and on an irregular basis.

This is a preview of subscription content, log in via an institution to check access.

Access this article

Price excludes VAT (USA)
Tax calculation will be finalised during checkout.

Instant access to the full article PDF.

Institutional subscriptions

Fig. 1
Fig. 2
Fig. 3

Similar content being viewed by others

References

  • AFNOR (1996) Qualité de l’eau—Dosage des matières en suspension—Méthode par filtration sur filtre en fibres de verre. In: AFNOR (ed) Qualité de l’eau—6e édition Tome 2—Analyses organoleptiques—Mesures Physico-chimiques—Paramètres globaux—Composés organiques. AFNOR, Paris, pp 101–110

    Google Scholar 

  • Agritox database. Available at http://www.dive.afssa.fr/agritox/php/fiches.php. Accessed 2 May 2012

  • Ahel M, Evans KM, Fileman TW, Mantoura RFC (1992) Determination of atrazine and simazine in estuarine samples by high-resolution gas chromatography and nitrogen selective detection. Anal Chim Acta 268:195–204

    Article  CAS  Google Scholar 

  • Altenburger R, Backhaus T, Boedeker W, Faust M, Scholze M, Grimme LH (2000) Predictability of the toxicity of multiple chemical mixtures to Vibrio fischeri: mixtures composed of similarly acting chemicals. Environ Toxicol Chem 19:2341–2347

    CAS  Google Scholar 

  • Aminot A, Chaussepied M (1983) Manuel des analyses chimiques en milieu marin. CNEXO, Brest

  • Aminot A, Kerouel R (2004) Hydrologie des écosystèmes marins: Paramètres et analyses. Editions Quae, Paris

    Google Scholar 

  • Arrhenius A, Grönvall F, Scholze M, Backhaus T, Blanck H (2004) Predictability of the mixture toxicity of 12 similarly acting congeneric inhibitors of photosystem II in marine periphyton and epipsammon communities. Aquat Toxicol 68:351–367

    Article  CAS  Google Scholar 

  • Babut M, Bonnet C, Bray M, Flammarion P, Garric J, Golaszewski G (2003) Developing environmental quality standards for various pesticides and priority pollutants for French freshwaters. J Environ Manage 69:139–147

    Article  Google Scholar 

  • Backhaus T, Altenburger R, Boedeker W, Faust M, Scholze M, Grimme LH (2000) Predictability of the toxicity of multiple mixture of dissimilarly acting chemicals to Vibrio fischeri. Environ Toxicol Chem 19:2348–2356

    CAS  Google Scholar 

  • Backhaus T, Faust M, Scholze M, Gramatica P, Vighi M, Grimme LH (2004) Joint algal toxicity of phenylurea herbicides is equally predictable by concentration addition and independent action. Environ Toxicol Chem 23:258–264

    Article  CAS  Google Scholar 

  • Bottoni P, Keizer J, Funari E (1996) Leaching indices of some major triazine metabolites. Chemosphere 32:1401–1411

    Article  CAS  Google Scholar 

  • Buisson S, Bouchart V, Guerlet E, Malas JP, Costil K (2008) Level of contamination and impact of pesticides in cupped oyster, Crassostrea gigas, reared in a shellfish production area in Normandy (France). J Environ Sci Health B 43:655–664

    Article  CAS  Google Scholar 

  • Carafa R, Wollgast J, Canuti E, Ligthart J, Dueri S, Hanke G, Eisenreich SJ, Viaroli P, Zaldívar JM (2007) Seasonal variations of selected herbicides and related metabolites in water, sediment, seaweed and clams in the Sacca di Goro coastal lagoon (Northern Adriatic). Chemosphere 69:1625–1637

    Article  CAS  Google Scholar 

  • Chapman PM, Wang F (2001) Assessing sediment contamination in estuaries. Environ Toxicol Chem 20:3–22

    Article  CAS  Google Scholar 

  • Chesworth JC, Donkin ME, Brown MT (2004) The interactive effects of the antifouling herbicides Irgarol 1051 and diuron on the seagrass Zostera marina (L.). Aquat Toxicol 66:293–305

    Article  CAS  Google Scholar 

  • Chèvre N, Loepfe C, Singer H, Stamm C, Fenner K, Escher BI (2006) Including mixtures in the determination of water quality criteria for herbicides in surface water. Environ Sci Technol 40:426–435

    Article  Google Scholar 

  • Dahl B, Blanck H (1996) Toxic effects of the antifouling agent Irgarol 1051 on periphyton communities in coastal water microcosms. Mar Pollut Bull 32:342–350

    Article  CAS  Google Scholar 

  • Di Landa G, Parrella L, Avagliano S, Ansanelli G, Maiello E, Cremisini C (2009) Assessment of the potential ecological risks posed by antifouling booster biocides to the marine ecosystem of the Gulf of Napoli (Italy). Water Air Soil Pollut 200:305–321

    Article  CAS  Google Scholar 

  • Duboudin C, Ciffroy P, Magaud H (2004) Effects of data manipulation and statistical methods on species sensitivity distribution. Environ Toxicol Chem 23:489–499

    Article  CAS  Google Scholar 

  • ECOTOX (ECOTOXicology) database. Available at http://www.epa.gov/ecotox. Accessed on 30 April 2012

  • EU (2008) Directive 2008/105/EC of the European Parliament and of the Council of 16 December 2008 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. Official Journal of the European Union L 384/84. Available at http://eur-lex.europa.eu/LexUriServ/LexUriServ.do?uri=OJ:L:2008:348:0084:0097:EN:PDF. Accessed on 30 April 2012

  • Farcy E, Burgeot Th, Haberkorn H, Auffret M, Lagadic L, Allenou J-P, Budzinski H, Mazzella N, Heydorff M, Menard D, Mondeguer F, Caquet Th (2012) Biomarkers fluctuations in the blue mussel Mytilus edulis L. in the Vilaine estuary, South Brittany, France. Environ Sci Pollut Res (in press)

  • Faust M, Altenburger R, Boedecker W, Grimme LH (1994) Algal toxicity of binary combinations of pesticides. Bull Environ Contam Toxicol 53:134–141

    Article  CAS  Google Scholar 

  • Faust M, Altenburger R, Backhaus T, Blanck H, Boedeker W, Gramatica P, Hamer V, Scholze M, Vighi M, Grimme LH (2001) Predicting the joint algal toxicity of multicomponent s-triazine mixtures at low-effect concentrations of individual toxicants. Aquat Toxicol 56:13–32

    Article  CAS  Google Scholar 

  • Ferrer I, Barceló D (1999) Simultaneous determination of antifouling herbicides in marina water samples by on-line solid-phase extraction followed by liquid chromatography–mass spectrometry. J Chromatogr A 854:197–206

    Article  CAS  Google Scholar 

  • Footprint Pesticide Properties DataBase. Available at http://sitem.herts.ac.uk/aeru/footprint/index2.htm. Accessed 2 May 2012

  • Hall LW, Gardinali P (2004) Ecological risk assessment for Irgarol 1051 and its major metabolite in United States surface waters. Hum Ecol Risk Assess 10:525–542

    Article  CAS  Google Scholar 

  • Hall LW Jr, Giddings JM, Solomon KR, Balcomb R (1999) An ecological risk assessment for the use of Irgarol 1051 as an algaecide for antifoulant paints. Crit Rev Toxicol 29:367–437

    CAS  Google Scholar 

  • Haynes D, Muller J, Carter S (2000) Pesticide and herbicide residues in sediments and seagrasses from the Great Barrier Reef world heritage area and Queensland coast. Mar Pollut Bull 41:279–287

    Article  CAS  Google Scholar 

  • Johnson LL, Landahl JT, Kubin LA, Horness BH, Myers MS, Collier TK, Stein JE (1998) Assessing the effects of anthropogenic stressors on Puget Sound flatfish populations. J Sea Res 39:125–137

    Article  Google Scholar 

  • Junghans M, Backhaus T, Faust M, Scholze M, Grimme LH (2003) Predictability of combined effects of eight chloroacetanilide herbicides on algal reproduction. Pest Manag Sci 59:1101–1110

    Article  CAS  Google Scholar 

  • KEMI (2006) Rapport 2/06 Kemiska ämnen i båtbottenfärger—en undersökning av koppar, zink och Irgarol 1051 runt Bullandö marina 2004. Available at http://www.kemi.se/Documents/Publikationer/Trycksaker/Rapporter/Rapport2_06.pdf. Accessed 3 May 2012

  • Leung KMY, Morritt D, Wheeler JR, Whitehouse P, Sorokin N, Toy R, Holt M, Crane M (2001) Can saltwater toxicity be predicted from freshwater data? Mar Pollut Bull 42:1007–1013

    Article  CAS  Google Scholar 

  • Lewis SE, Brodie JE, Bainbridge ZT, Rohde KW, Davis AM, Masters BL, Maughan M, Devlin MJ, Mueller JF, Schaffelke B (2009) Herbicides: a new threat to the Great Barrier Reef. Environ Pollut 157:2470–2484

    Article  CAS  Google Scholar 

  • Lorenzen CJ (1967) Determination of chlorophyll and pheopigments: spectrophotometric equations. Limnol Oceanog 12:343–346

    Article  CAS  Google Scholar 

  • Maltby L, Blake N, Brock TCM, Van den Brink PJ (2005) Insecticide species sensitivity distributions: importance of test species selection and relevance to aquatic ecosystems. Environ Toxicol Chem 24:379–388

    Article  CAS  Google Scholar 

  • Mazzella N, Delmas F, Delest B, Méchin B, Madigou C, Allenou JP, Gabellec R, Caquet T (2009) Investigation of the matrix effects on a HPLC-ESI-MS/MS method and application for monitoring triazine, phenylurea and chloroacetanilide concentrations in fresh and estuarine waters. J Environ Monitor 11:108–115

    Article  CAS  Google Scholar 

  • Munaron D, Dubernet JF, Delmas F, Stanisiere JY, Scribe P (2006) Assessment of the quantities of herbicides and nutrients brought down by the river Charente to the coast and modelling of the dispersion of atrazine in the Marennes-Oleron bay. Cah Biol Mar 47:85–92

    Google Scholar 

  • Newman MC, Ownby DR, Mézin LCA, Powell DC, Christensen TRL, Lerberg SB, Anderson BA (2000) Applying species-sensitivity distributions in ecological risk assessment: assumptions of distribution type and sufficient numbers of species. Environ Toxicol Chem 19:508–515

    CAS  Google Scholar 

  • Noppe H, Ghekiere A, Verslycke T, De Wulf E, Verheyden K, Monteyne E, Polfliet K, van Caeter P, Janssen CR, De Brabander HF (2007) Distribution and ecotoxicity of chlorotriazines in the Scheldt Estuary (B-Nl). Environ Pollut 147:668–676

    Article  CAS  Google Scholar 

  • Okamura H, Nishida T, Ono Y, Shim WJ (2003) Phytotoxic effects of antifouling compounds on nontarget plant species. Bull Environ Contam Toxicol 71:881–886

    Article  CAS  Google Scholar 

  • Omae I (2003) Organotin antifouling paints and their alternatives. Appl Organometal Chem 17:81–105

    Article  CAS  Google Scholar 

  • Owen R, Knap A, Toaspern M, Carbery K (2002) Inhibition of coral photosynthesis by the antifouling herbicide Irgarol 1051. Mar Pollut Bull 44:623–632

    Article  CAS  Google Scholar 

  • Power M, Attrill MJ, Thomas RM (1999) Trends in agricultural pesticide (atrazine, lindane, simazine) concentrations in the Thames Estuary. Environ Pollut 104:31–39

    Article  CAS  Google Scholar 

  • Readman JW, Albanis TA, Barcelo D, Galassi S, Tronczynski J, Gabrielides GP (1993) Herbicide contamination of Mediterranean estuarine waters: results from a MED POL pilot survey. Mar Pollut Bull 26:613–619

    Article  CAS  Google Scholar 

  • RNO (2004) Surveillance du Milieu Marin. Travaux du RNO. Edition 2004. Ifremer et Ministère de l’Ecologie et du Développement Durable. Available at http://envlit.ifremer.fr/content/download/27644/224815/version/1/file/rno04.pdf. Accessed 1 May 2012

  • Rodriguez Romero J (2011) Cybutryne EQS dossier 2011. Available at http://circa.europa.eu/Public/irc/env/wfd/library?l=/framework_directive/thematic_documents/priority_substances/supporting_substances/eqs_dossiers/cybutryne_2011pdf/_EN_1.0_&a=i. Accessed 30 April 2012

  • Sánchez-Rodríguez A, Sosa-Ferrera Z, Santana-del Pino A, Santana-Rodríguez JJ (2011) Probabilistic risk assessment of common booster biocides in surface waters of the harbours of Gran Canaria (Spain). Mar Pollut Bull 62:985–991

    Article  Google Scholar 

  • Shaw M, Müller JF (2005) Preliminary evaluation of the occurrence of herbicides and PAHs in the wet tropics region of the Great Barrier Reef, Australia, using passive samplers. Mar Pollut Bull 51:876–881

    Article  CAS  Google Scholar 

  • Smith EP, Cairns J Jr (1993) Extrapolation methods for setting ecological standards for water quality: statistical and ecological concerns. Ecotoxicology 2:203–219

    Article  Google Scholar 

  • SOES (2011) Bilan de présence des micropolluants dans les milieux aquatiques continentaux, période 2007–2009. Études & documents no. 54—octobre 2011. Available at http://www.statistiques.developpement-durable.gouv.fr/fileadmin/documents/Produits_editoriaux/Publications/Etudes_et_documents/2011/E&D54_p53corrigee_janv2012.pdf. Accessed 30 April 2012

  • Steen RJCA, van der Vaart J, Hiep M, Van Hattum B, Cofino WP, Brinkman UAT (2001) Gross fluxes and estuarine behaviour of pesticides in the Scheldt Estuary (1995–1997). Environ Pollut 115:65–79

    Article  CAS  Google Scholar 

  • Van Leeuwen CJ (1990) Ecotoxicological effect assessment in the Netherlands, recent developments. Environ Manag 14:779–792

    Article  Google Scholar 

  • van Wezel AP, van Vlaardingen P (2004) Environmental risk limits for antifouling substances. Aquat Toxicol 66:427–444

    Article  Google Scholar 

  • Wheeler JR, Leung KMY, Morritt D, Sorokin N, Roger H, Toy R, Holt M, Whitehouse P, Crane M (2002) Freshwater to saltwater toxicity extrapolation using species sensitivity distributions. Environ Toxicol Chem 21:2459–2467

    Article  CAS  Google Scholar 

  • Zhang AQ, Leung KMY, Kwok KWH, Bao VWW, Lam MHW (2008) Toxicities of antifouling biocide Irgarol 1051 and its major degraded product to marine primary producers. Mar Pollut Bull 57:575–586

    Article  CAS  Google Scholar 

Download references

Acknowledgments

This program was funded by the French National Research Agency in the framework of the program Ecotoxicology and Ecodynamics of Contaminants (ECODYN). The authors wish to thank the personnel of the Institution d’Aménagement de la Vilaine for giving access to the Arzal dam and to their laboratory facilities. In particular, the authors gratefully acknowledge V. Véron and L. Audic for providing logistic support to their activities.

Author information

Authors and Affiliations

Authors

Corresponding author

Correspondence to Th. Caquet.

Additional information

Responsible editor: Hongwen Sun

Electronic supplementary material

Below is the link to the electronic supplementary material.

Online Resource 1

Monthly cumulative rainfall (in mm) recorded in Meteo France station in Theix in 2006 and 2007 (PDF 9 kb)

Online Resource 2

Daily flow (in m3/s) at the outlet of Arzal dam during the monitoring period in 2006 and 2007 (PDF 14 kb)

Online Resource 3

Additional information on the analytical methods used for this study (PDF 26 kb)

Online Resource 4

Data used for the construction of the SSDs (PDF 98 kb)

Online Resource 5

Results of the residue analysis for the various compounds analyzed in the water samples collected in the different sampling sites (PDF 39 kb)

Rights and permissions

Reprints and permissions

About this article

Cite this article

Caquet, T., Roucaute, M., Mazzella, N. et al. Risk assessment of herbicides and booster biocides along estuarine continuums in the Bay of Vilaine area (Brittany, France). Environ Sci Pollut Res 20, 651–666 (2013). https://doi.org/10.1007/s11356-012-1171-y

Download citation

  • Received:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1007/s11356-012-1171-y

Keywords

Navigation