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

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

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 www.norman-network.net

NORMAN Position paper “Passive sampling of emerging pollutants in the aquatic environment: state of the art and perspectives” Document is available at www.norman-network.net 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

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 - 19 participants pharmaceuticals – 17 participants steroid hormones – 14 participants triclosan - 8 participants bisphenol A - 11 participants PFOA, PFOS - 8 participants PBDE - 16 participants

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

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

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

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.

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) 2006-2007. Part 1: Objectives, Design and Realization, . http://www.ices.dk/products/CMdocs/CM-2007/J/J0207.pdf

Participating institutes 35 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.

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

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 2001. This was added to an existing musselwatch program of actively deployed mussels.

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

Recent and planned activities in Europe A biannual scientific conference www.ipsw.eu 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

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