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![Page 1: The chemical monitoring of organic pollutants using passive samplers within the framework of the PORTONOVO project (water quality in harbours of the Atlantic.](https://reader033.fdocuments.us/reader033/viewer/2022051417/56649cd65503460f9499dfd9/html5/thumbnails/1.jpg)
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
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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"
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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
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Ports associated to the project
Belfast
Cherbourg
Falmouth
BordeauxSantander
Portimao
Aveiro
Huelva
very different hydromorphological et socio-economical characteristics
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Interconnected activities
EPOC mainly involved in activity 6, but also in activity 7
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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)
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Act. 4 - Environmental Risk Assessment: IH Cantabria (SP)
48% 52%
Methodology to identify and characterise environnemental hazards in port areas (point and diffuse sources)
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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
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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)
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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)
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Passive samplers
SPMD Semi Permeable Membrane Device
hydrophobic organic compounds
POCISPolar Organic Chemical Integrative Sampler
hydrophilic organic compounds
Silicone strips
hydrophobic organic compounds
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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
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• 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
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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%
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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)
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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%
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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)
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Port of Portimao (Portugal)
WWTP
port authority buildings
Marina de Boca do Rio
Arade River
PAB MBR
In collaboration with the University of Algarve
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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%)
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Port of SantanderIn collaboration with IH Cantabria
POCIS
SPMD
Silicone strips
Analyses in progress
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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)
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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
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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)
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Thank you for your attention!
www.portonovoproject.org