1. Passive Sampling: From Research to an Innovation Transfer for the WFD CIS by B. Vrana, F. Smedes, V. Dulio presented by B. Gawlik in the context of the NORMAN/JRC Collaboration Agreement

2. Passive samplers Alternative to spot sampling
Provide time-weighted average (TWA) concentrations over longer deployment time
Are non-mechanical (based on diffusion), easy-to-deploy and require no maintenance
Range of application environments: sites with limited security; remote sites with little/no infrastructure
Are not dependent on a power or other energy supply
Used for short (days) or long term (months) monitoring

3. Activities of NORMAN network in passive sampling 2009-2011
An expert group meeting in 2009
A position paper “Passive sampling of emerging pollutants in the aquatic environment: state of the art and perspectives” in 2010
An collaborative field study “Chemical Monitoring On Site (CM Onsite) organised by NORMAN Association and DG JRC in support of CIS WFD” in 2011

4. NORMAN Position paper “Passive sampling of emerging pollutants in the aquatic environment: state of the art and perspectives”
Document is available at
Application in sediment monitoring
Application in monitoring of contaminants in biota
Application in ecotoxicity assessment
Passive samplers as mimics for bioconcentration
Which passive sampler suits which bioassay?
The link between biological and chemical analysis
Effect-directed analysis
How does the bioassay response in passive sampler extracts relate to sampler exposure conditions?
Quality assurance, quality control and normation
Application of passive samplers in regulatory monitoring
Future trends

5. Interlaboratory study on passive sampling of emerging substances
a sampler comparison exercise
present variability in data by comparing results from various passive samplers sent by participating laboratories exposed to water at a single (reference) site – a WWTP
extended to cover individual aspects in the passive sampling process
analytical comparability
comparison with spot sampling
Target substances:
polar pesticides participants
pharmaceuticals – 17 participants
steroid hormones – 14 participants
triclosan participants
bisphenol A participants
PFOA, PFOS participants
PBDE participants

6. Study design 1. Passive samplers from participants
for selected analyte/analytes
Participant 1
Sampler 1
Sampler 1
Sampler 2
Participant 2
Sampler 2
Coordinator
Sampler 3
Sampler 4
Sampler 3
Participant 3
Sampling site -
sampler exposure
Sampler 4
Participant 4
Report to database
ng/sampler of compound A
ng/cm2 sampler of compound A
ng/L water of compound A
calculation procedure for compound A
Quasimeme

7. Study design 2. Passive samplers from coordinator
for selected analyte/analytes 3.
Central laboratory
Participant 1 3.
Provided
sampler
Provided
sampler 3. 2.
Provided
sampler
Participant 2
Provided
sampler
Provided
sampler
Coordinator
Provided
sampler
Provided
sampler 3.
Provided
sampler
Participant 3
Buy or prepare 1.
Sampling site -
sampler exposure 3.
Provided
sampler
Participant 4
Provided
sampler
Provided
sampler
Provided
sampler
Provided
sampler
Report to database
ng/sampler of compound A
ng/cm2 sampler of compound A
ng/L water of compound A
calculation procedure
Report to database
ng/sampler of compound A
ng/cm2 sampler of compound A
ng/L water of compound A
calculation procedure
Quasimeme

8. Interlaboratory study on passive sampling of emerging substances
3 rounds, May-August 2011
2012 – a workshop will be organised to disseminate results.

9. Examples of applicability of passive samplers in monitoring under WFD
Assessment of spatial distribution of ultra trace contaminants e.g. in coastal and transitional waters
Monitoring long term trends of bioaccumulating compounds
Compliance checking with EQS
Measurement of activity and fugacity of compounds in the aqueous phase - a monitoring tool to support modelling of pollutant fate
1. Spatial distribution of contaminants e.g. in coastal and transitional waters for priority compounds can be assessed (see following slides from the Passive Sampling Trial Survey 2006 ).
Passive samplers can be used perfectly for monitoring long term trends of bioaccumulating compounds, with much less random data variability than obtained with biota or sediment analysis.
Compliance checking
3.a) Compliance checking with EQS for water is straightforward for compounds predominantly present in water in the dissolved phase -
polar compounds. However, for those compounds more information is needed on uncertainty of reported concentrations. Studies like the NORMAN interlaboratory exercise will bring more confidence.
3.b) Compliance checking with EQS in water for metals is possible, since there is an evidence that DGT technique can provide concentrations of the 0.45um filtered equivalent concentration.
3.c) Compliance checking with EQS for water for hydrophobic compounds using PS is complicated by the fact that EQS are derived for whole water. PS measure dissolved concentrations. Still, passive samplers are able to measure representative (time integrated) ultra trace concentrations in situations where low volume spot sampling fails to detect the compounds completely. Rules need to be established that will allow to apply PS in compliance checking.
3d). Passive samplers can be well applied in compliance checking with EQS derived for biota for bioaccumulating compounds. Passive samplers for hydrophobic compounds such as silicone rubber are excellent surrogates for biota at the lowest trophic level (such as mussels) and a long term comparisons are available (see following Foppe`s slides).
4. Passive samplers provide information on activity and fugacity of compounds in the aqueous phase and can be used as a monitoring tool to support modelling of pollutant fate.

10. ICES Passive Sampling Trial Survey in 2006, The Objectives
to transfer knowledge of PS more widely within the ICES community.
to gain experience in the use of passive samplers.
to estimate the contribution of the analytical component to total variability.
to compare data from passive samplers in water with mussels over a large geographical range in order to validate the environmental relevance of passive sampling data.
to gain further information towards the validation of the use of passive samplers in sediment.
In 2006 the ICES Passive Sampling Trial Survey was organised by the ICES Marine Chemistry working group and the Working Group on Marine Sediments in relation to pollution.
The objectives are listed in the slide and some results related the yellow shaded item will be shown.
Silicone rubber samplers were used that were supplied by the Central organising laboratory (National institute for Coastal and Marine anagement/RIKZ now include in the Centre for Water Services/Waterdienst)
Design is described in :
F. Smedes, I. M. Davies, and J. Tronczynski, ICES CM 2007/J:02, ICES Passive sampling trial survey for water and sediment (PSTS) Part 1: Objectives, Design and Realization, .

11. Participating institutes35 40 45 50 55 60 65 70 75
-25
-20
-15
-10 -5 5 10 15 20 25 30
RIKZ
Inst Ocean
Esp
IFREMER
IMARES
Univ of
Queensl
Australa
Hydr
Inst
Mar Inst
FRS
NIVA
NERI
IOW
BSH
MUMM
Queenslan
Australia
12 laboratories in Europe and one in Australia joined the exercise.
Each laboratory deployed samplers, mostly two stations, and where possible they also deployed mussels in parallel or alternatively collected native mussels.

12. Sampler recovery
After exposure sampler are fouled to different degrees. This does not affect the principles of the uptake as long this is in situ calibrated by through the release of PRCs

13. A decade of monitoring with PS in the Netherlands
From 2001 passive samplers were exposed parallel to mussels
8 stations
2 times a year (autumn and winter )
Monitoring program executed by the RIKZ, since 2008 merged
with the Centre for Water Services, Lelystad, The Netherlands
The Netherland already conduct a monitoring program with passive sampling since This was added to an existing musselwatch program of actively deployed mussels.

14. Stations PCB 153 in mussels and water
dry weight) ) )
droog
droog
dissolved
opgelost
opgelost ( ( ( 3 3 ” ” 2 2
mussel
mossel
mossel
freely
vrij
vrij 6 6
25 pg/L “
25 pg/L “
50 µg/kg
50 µg/kg
50 µg/kg
25 pg/L 7 7
Rhine
Rhine 8 8
This figure show the location of the sampling stations as well as a first impression of the distribution of PCB 153 concentrations on that stations.
The freely dissolved concentration derived from passive sampling and that in the mussels deployed in parallel (autumn 2003) 4 4 5 5
Meuse
Meuse
Start Conc 17 µg/kg
Scheldt
Scheldt
Scheldt
Scheldt

15. Recent and planned activities in Europe
A biannual scientific conference
ISO 5667/23 - a guidance is available
In 2010 the Centre for Water Services, Lelystad, The Netherlands, had a study conducted that evaluated the application of passive sampling for WFD monitoring a)
2011: a technical guidance document for the application of passive samplers: coordinated by Cemagref in the framework of the programme of activities of AQUAREF b)
An Innovation Transfer Event in 2012 organised by NORMAN + JRC
Document is in Dutch but a translation is in progress
Document is in French

16. Possible future actions at EU level Pan European monitoring campaigns
build up a long term monitoring network at important aquatic "surveillance" monitoring sites (major rivers, lakes, estuaries and coastal areas) in Europe in a similar way like POPs are being monitored using atmospheric passive samplers under Stockholm convention  Watch List Sites?
look at long term trends for bioaccumulative compounds - fulfillment of the no deterioration objective
campaigns inculding side by side monitoring with biota and passive samplers (biomimetic sampling) - activities already running in the Netherlands and could be extended to other member states
screening campaigns - similar like pan European campaigns organised by DG JRC for various matrixes. Not only targeted at compounds but possibly also at specific toxicological effects (combination with bioassays). Passive samplers better preserve sampled contaminants than water samples and are easier to transport.
NORMAN association provides the scientific expertise. JRC facilitates the policy-support link and Member States need to be active