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 Dévier1, Nathalie Tapie1, Angel Belles1, Karyn Le Menach1, Maria Gonzalez-Rey2, Maria Bebianno2, Beatriz Echavarri Erasun3, José Antonio

Juanes de la Peña3, Hélène Budzinski1

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

Portonovo Portonovo ProjectProjectwww.portonovoproject.or

g

Atlantic Area Programme 2007 – 2013 : Interreg project PORTONOVOPriority 2 - Marine Environment & Renewable EnergiesFinancing: 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 modifie

d

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"

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

Ports associated to the project

Belfast

Cherbourg

Falmouth

BordeauxSantander

Portimao

Aveiro

Huelva

very different hydromorphological et socio-economical characteristics

Interconnected activities

EPOC mainly involved in activity 6, but also in activity 7

3) Establishment of management zonesActivities ERA & Indicators - Monitoring

1) Identification of HMWB zones

Salinity <30 ‰ <30 ‰ >30 ‰ >30 ‰Renewal rate Low (> 7days) High (≤ 7 days) Low (> 7days) High (≤ 7 days)

Type T1 T2 C1 C2

Coastal watersTransitional watersHMWB 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)

Act. 4 - Environmental Risk Assessment: IH Cantabria (SP)

48% 52%

Methodology to identify and characterise environnemental hazards in port areas (point and diffuse sources)

ECOLOGICAL POTENTIAL CHEMICAL STATUS

Biological indicators

Physico-chemical indicators

Invertebrates

Chlorophyll a

Macroalgaes

Angiosperm

General conditions

Specific pollutants

Water

Transparency

Oxygenation

Nutrients

Total Hydrocarbons

Other pollutants (water basin district)

Specific pollutants

Sediment

Organic conditions

Chemical conditions

Bioassays

Biomarkers

Priority substances

Annex X WFD/ Member state

Water Sediment Biota

Environm.qualitystandards (EQS)

Passive samplers

Other pollutants (water basin district)

EQS EQS

Bioaccumulation

ValvometryHFNI

Phytoplancton

Fish

ECOLOGICAL POTENTIAL CHEMICAL STATUS

Biological indicators

Physico-chemical indicators

Invertebrates

Chlorophyll a

Macroalgaes

Angiosperm

General conditions

Specific pollutants

Water

Transparency

Oxygenation

Nutrients

Total Hydrocarbons

Other pollutants (water basin district)

Specific pollutants

Sediment

Organic conditions

Chemical conditions

Bioassays

Biomarkers

Priority substances

Annex X WFD/ Member state

Water Sediment Biota

Environm.qualitystandards (EQS)

Passive samplers

Other pollutants (water basin district)

EQS EQS

Bioaccumulation

ValvometryHFNI

Phytoplancton

Fish

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

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)

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)

Time

Co

nce

ntr

atio

n

From spot sampling(snapshot concentration) …

… To integrative sampling(time-weighted average concentration)

Time

Co

nce

ntr

atio

n

From spot sampling(snapshot concentration) …

… To integrative sampling(time-weighted average concentration)

Passive samplers

SPMD Semi Permeable Membrane Device

hydrophobic organic compounds

POCISPolar Organic Chemical Integrative Sampler

hydrophilic organic compounds

Silicone strips

hydrophobic organic compounds

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

Pauillac

Bordeaux

Le Verdon

Blaye

Ambes

Bassens

Pauillac

Bordeaux

Le Verdon

Blaye

Ambes

Bassens

• POCIS PRC (Performance Reference Compounds)• 49 Pesticides + 21 Pharmaceuticals • Continuous since April 2010 (Bordeaux) or summer/winter (Pauillac)

Fungicides 5Insecticides 4Herbicides 28Pesticides metabolites 12NSAIDs 7Antidepressants 4Anxiolytics 4Bronchodilatators 4Antilipemiant 1Alkaloid 1

Variable and diluted environment making the chemical quality assessment very difficult (complex transferts, tidal dynamics, particulate load...)

Passive sampling

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%

Ibuprofen8%Paracetamol

41%

Aspirin25%

Others (minor.)

Naproxen5%

Gemfibrozil1%

Ketoprofen6%

Carbamazepine7%

Nordiazepam

Diclofenac6%

Metolachlor ESA42%

Metolachlor OA11%

S-Metolachlor26%

Triazines & metabo.

8%

Chlorotoluron1%

Diuron2%

Thiamethoxam4%

Propiconazole1%

Carbetamide1%

Carbendazim2%Imidacloprid

2%

0

100

200

300

400

500

600

700

800

Apr-10 May-10 Jun-10 Jul-10 Aug-10 Sep-10 Oct-10 Nov-10 Dec-10 Jan-11 Feb-11

Co

nc

en

tra

tio

n i

n n

g/L

Metolachlor OA

Metolachlor ESA

Metolachlor

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

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%

Ibuprofen8%Paracetamol

41%

Aspirin25%

Others (minor.)

Naproxen5%

Gemfibrozil1%

Ketoprofen6%

Carbamazepine7%

Nordiazepam

Diclofenac6%

Metolachlor ESA42%

Metolachlor OA11%

S-Metolachlor26%

Triazines & metabo.

8%

Chlorotoluron1%

Diuron2%

Thiamethoxam4%

Propiconazole1%

Carbetamide1%

Carbendazim2%Imidacloprid

2%

Detection of very low concentration levels (POCIS)

Effects of these chemical coktails on aquatic organisms ?

PesticidesConcentration

(ng/L)Pharmaceuticals

Concentration (ng/L)

Irgarol 1.43 Gemfibrozil 3.20Linuron 0.37 Bromazepam 0.86Terbutryn 1.64 Fluoxetine 1.26Promethryn 0.46 Alprazolam 0.86Terbutylazine 1.12 Diazepam 0.57Propazine 0.14 Amitriptiline 0.56Ametryn 0.13Nicosulfuron 0.68 Bordeaux, August 2010Hexazinone 0.89Chlorotoluron 1.35Isoproturon 0.73134-dichlorodiphenylurea 1.07Metsulfuron-methyl 0.13Carbofuran 0.14Flazasulfuron 0.10Prosulfuron 0.17Methiocarb 0.03Azoxystrobin 1.37Flusilazole 1.15Diflufenican 0.53Fluazifop-p-butyl 0.03

(Minority compounds only)

Port of Portimao (Portugal)

WWTP

port authority buildings

Marina de Boca do Rio

Arade River

PAB MBR

In collaboration with the University of Algarve

0

10

20

30

40

50

Triaz.&

met

abo.

Imid

aclo

prid

Carben

dazim

DMST

Terbut

hrin

Diuro

n

Irgar

ol

DMSA

Co

nc

en

tra

tio

n (

ng

/L)

MBR Aug. MBR Sept. MBR Oct.

PAB Aug. PAB Sept. PAB Oct.

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%)

Port of SantanderIn collaboration with IH Cantabria

POCIS

SPMD

Silicone strips

Analyses in progress

0

1

2

3

4

5

6

7

8

Atrazin

e

Atrazin

e-2-

hydr

oxy

Terbu

thyla

zine

S-Met

olach

lor

Met

olach

lor O

A

Met

olach

lor E

SA

DMST

Terbu

thrin

Diuro

n

Irgar

ol

DMSA

Co

nc

en

tra

tio

n (

ng

/L) POCIS nylon

POCIS PES

Main pesticides detected in POCIS (1 month)

PAHs in SPMD (1 month)

[PAH] in ng/LSPMD

(CV<7%)

Filtered surface water

(03/02/2011)

Filtered surface water

(24/02/2011)Naphthalene <3 2.7 4.2Acenaphthylene 0.24 nd 0.5Acenaphthene 0.47 0.5 0.8Fluorene 1.02 0.6 1.2Dibenzothiophene <0.1 0.7 0.6Phenanthrene 1.69 1.9 3.9Anthracene 0.12 0.1 0.2Fluoranthene 1.64 1.3 4.4Pyrene 0.90 0.9 2.5Benzo(a)anthracene 0.12 0.5 0.2Triphenylene + Chrysene 0.33 1.0 0.92,1-Benzonaphtothiophene 0.07 0.3 0.2Benzo(b)fluoranthene + Benzo(k)fluoranthene + Benzo(j)fluoranthene

0.92 nd nd

Benzo(e)pyrene 0.33 nd ndBenzo(a)pyrene 0.21 nd ndPerylene <0.1 nd ndIndeno(123-cd)pyrene 0.14 nd ndDibenzo(ah)anthracene + Dibenzo(ac)anthracene

<0.1 nd nd

Benzo(ghi)perylene 0.12 nd ndTotal PAHs 8.30 10 20

Proposed revised EQS probably by far lower than actually

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)

Thank you for your attention!

www.portonovoproject.org