1. The chemical monitoring of organic pollutants using passive samplers within the framework of the PORTONOVO project (water quality in harbours of the Atlantic area) Marie-Hélène Dévier 1, Nathalie Tapie 1, Angel Belles 1, Karyn Le Menach 1, Maria Gonzalez-Rey 2, Maria Bebianno 2, Beatriz Echavarri Erasun 3, José Antonio Juanes de la Peña 3, Hélène Budzinski 1 1 EPOC (UMR 5805), LPTC, CNRS, University of Bordeaux 1, Talence, France; 2 IH Cantabria, University of Cantabria, 39005 Santander, Spain 3 CIMA, University of Algarve, 8005-139 Faro, Portugal

2. Portonovo Project www.portonovoproject.org Atlantic Area Programme 2007 – 2013 : Interreg project PORTONOVO Priority 2 - Marine Environment & Renewable Energies Financing: 1 800 000 € (60% ERDF) PORTONOVO (Nov. 2009 – Feb. 2012): to standardize a methodology for the water quality management in port areas all over along the Atlantic Area  Installation of a common tool allowing a sustainable management of harbour waters ("Decision Supporting System", DSS) Economic development Hydromorphological changes "Good ecological potential" "Good chemical status" Ports Water Framework Directive (WFD) Heavily modified water bodies (HMWB) What has to be protected? What does it have to be protected from? How can it be protected? "Good ecological status" "Good chemical status"

3.  Lead partner: University of Cantabria (Santander, Spain) José A. Juanes de la Peña, Environmental Hydraulics Institute "IH Cantabria"  11 partners + 12 associated partners: - Spain: 3 partners (plus 2 associated partners) - France: 3 (+5) - Portugal: 3 (+3) - United Kingdom: 2 (+2) Partners of the project

4. Ports associated to the project Belfast Cherbourg Falmouth Bordeaux Santander Portimao Aveiro Huelva very different hydromorphological et socio-economical characteristics

5. Interconnected activities EPOC mainly involved in activity 6, but also in activity 7

6. 3) Establishment of management zones Activities ERA & Indicators - Monitoring 1) Identification of HMWB zones HMWB types: Act. 3 – Governance: Cherbourg Urban Community - CUC (FR) 2) Division in relation to the water renewal rate Act. 5 – Environmental modelling: Instituto Superior Técnico - IST (PT)

7. Act. 4 - Environmental Risk Assessment: IH Cantabria (SP) 48%52%  Methodology to identify and characterise environnemental hazards in port areas (point and diffuse sources)

8. Act. 6: Indicators and environmental monitoring: AZTI Tecnalia (SP) Which ones ? Support of new tools and of relevant indicators  Methodology for the evaluation of the water quality in port areas

9.  Installation of a tool allowing for the processing, storage and interchange of all information related with water quality under a decision making perspective  Validation of the methodology and DSS through case studies application Act. 7 - Decision Supporting System (DSS): Falmouth Harbour Commissioners (UK)

10. Passive sampling as complementary approach relevant to the chemical monitoring - Time-integrated average (TWA) concentrations and episodic events - Quantification of extremely low pollution levels in water, undetected using conventional spot sampling - Simplified logistics which permits to increase the number of sampling sites and the frequency of monitoring (as well as simplification of analyses)

11. Passive samplers SPMD Semi Permeable Membrane Device  hydrophobic organic compounds POCIS Polar Organic Chemical Integrative Sampler  hydrophilic organic compounds Silicone strips  hydrophobic organic compounds

12. Port of Bordeaux: Gironde estuary (France) 6 port terminals along 100 km

13. POCIS PRC (Performance Reference Compounds) 49 Pesticides + 21 Pharmaceuticals Continuous since April 2010 (Bordeaux) or summer/winter (Pauillac) Variable and diluted environment making the chemical quality assessment very difficult (complex transferts, tidal dynamics, particulate load...) Passive sampling

14. Most frequently detected compounds in Bordeaux (annual mean) Pesticides (frequency = 100% & max. concentrations > 10 ng/L) Pharmaceuticals (frequency = 90% & max concentrations > 2 ng/L) Minority pesticides: 5%Except caffein and theophylline > 50%

15. Seasonal variations of levels S-metolachor and its metabolites (Bordeaux)

16. Most frequently detected compounds in Bordeaux (annual mean) Pesticides (frequency = 100% & max. concentrations > 10 ng/L) Pharmaceuticals (frequency = 90% & max concentrations > 2 ng/L) Minority pesticides: 5%Except caffein and theophylline > 50%

17. Detection of very low concentration levels (POCIS) Effects of these chemical coktails on aquatic organisms ? (Minority compounds only)

18. Port of Portimao (Portugal) WWTP port authority buildings Marina de Boca do Rio Arade River PABMBR In collaboration with the University of Algarve

19. PAB MBR Main pesticides detected in POCIS during 3 months Also used as antifoulants (DMSA: dichlofluanid metabolite) Pharmaceuticals (POCIS): carbamazepine, paracetamol, ibuprofen, diclofenac, naproxen, gemfibrozil (1 - 100 ng/L), diazepam, nordiazepam, alprazolam, amitriptyline (0.1 - 1 ng/L) + caffein, theophylline (~70-80%)

20. Port of Santander In collaboration with IH Cantabria POCIS SPMD Silicone strips Analyses in progress

21. Main pesticides detected in POCIS (1 month)

22. PAHs in SPMD (1 month) Proposed revised EQS probably by far lower than actually

23. CONCLUSION Portonovo objective: Installation of a Decision Supporting System (DSS) for the balanced management of activities in harbour waters as well as a monitoring of the environmental quality in harbours along the Atlantic Area www.portonovoproject.org Passive sampling as complementary approach in the WFD: Confirmed interest of passive samplers for the chemical monitoring in the context of the WFD (other than logistics...):  Determination of TWA concentrations (although freely-dissolved conc.)  Detection of numerous pesticides and pharmaceuticals in port waters  Detection of pollutants undetected using conventional spot sampling (< 0.1 ng/L)  Detection of WFD priority pollutants (atrazine, simazine, diuron, isoproturon, PAHs) and some other pollutants, notably those included in the ongoing review of the WFD priority pollutants (irgarol, terbutryn, ibuprofen, diclofenac)

24. Thank you for your attention! www.portonovoproject.org