Dorothea Gilbert, Espen Eek, Naiara Berrojalbiz, Amy MP Oen and Hans Peter H. Arp. Norwegian Geotechnical Institute, Oslo

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1 Innovative passive sampling techniques at the sediment-water and air-water interface for monitoring the presence and fluxes of hydrophobic organic contaminants Dorothea Gilbert, Espen Eek, Naiara Berrojalbiz, Amy MP Oen and Hans Peter H. Arp Norwegian Geotechnical Institute, Oslo Norsk Vannforening: Innovative Vannovervåkningsmetoder 9. Mars 2017, Forskningsparken Oslo

2 Passive sampling silicone air silicone water biota silicone sediment

3 Passive sampling silicone air water sediment biota Advantages C pol is easy to measure one protocol for all compartments Comparison across media and thus information on direction of gradients Proportionality to bioavailability (C lipid )

4 EQS (µg/g) Passive sampling in Exposure Assessment EQS pol = K pol:w K OC EQS sed EQS pol = K pol:w EQS w EQS Environmental Quality Standard Mayer et al. 2014: Integr Envrion Assess Manag 10(2), pp

5 Contaminant uptake into polymers linear uptake C polymer equilibrium intermediate time C free = C pol K pol:w Mass of polymer Reichenberg et al. 2008, Chemistry Central Journal DOI: / X-2-8.

6 Cross-validation of passive sampler measurements by parallel deployment of different polymers in various thicknesses (1) Consistency check on the basis of C free C w,free = C PE /K PE:w C w,free = C PDMS /K PDMS:w CPE LDPE K PE:PDMS CPDMS silicone (2) Consistency check on the basis of K pol:pol C PDMS C PE = K PDMS:PE sediment water porewater sediment porewater sediment C PE / K PE:w = C free = C PDMS / K PDMS:w C free freely dissolved concentration in water or sediment pore water Gilbert et al.: Polymers as reference partitioning phase. Analytical Chemistry 2016, DOI: /acs.analchem.6b00393

7 Passive sampling in the Inner Oslofjord October 15 March 16 Industrial Harbor, Bekkelaget, 53m VEAS WWT, 120m

8 NGI s sediment porewater probe ES&T Letters 2015

9 LDPE and silicone passive samplers in different thicknesses PE PE 26 µm 51 µm PDMS PDMS 127 µm 356 µm Parallel deployment of LDPE (26 and 51 µm) and PDMS silicone ( µm) passive samplers.

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12 amount in polymer, n (ng) Equilibration in water Benzo[b+k]fluoranthene y = 1.418x R 2 = PE 26 µm PE 51 µm amount in polymer, n (ng) 5 y = 4.314x R 2 = PE 26 µm Benzo[a]pyrene PE 51 µm amount in polymer, n (ng) y = x R 2 = PE 26 µm PE 51 µm Pyrene amount in polymer, n (ng) Chrysene 0.5 Hexachlorobiphenyls Pentachlorobiphenyls 20 y = x 1.5 R with y = mx, the slope m equals the concentration (ng/g) = PE 26 µm PE 51 µm amount in polymer, n (ng) amount in polymer, n (ng) PCB 153 PCB

13 amount in polymer, n (ng) Equilibration in water Benzo[b+k]fluoranthene y = 1.418x R 2 = PE 26 µm PE 51 µm amount in polymer, n (ng) 5 y = 4.314x R 2 = PE 26 µm Benzo[a]pyrene PE 51 µm amount in polymer, n (ng) y = x R 2 = PE 26 µm PE 51 µm Pyrene amount in polymer, n (ng) y = x R 2 = PE 26 µm Chrysene PE 51 µm amount in polymer, n (ng) Pentachlorobiphenyls amount in polymer, n (ng) Hexachlorobiphenyls PCB 153 PCB

14 ,5 PAH profile across the sed-water interface ng/g PE 51 µm 12,5 26 µm water sediment ,5 2,5-2, ,5-27,5-32,5 In water: equilibrium for < 5-ring PAHs In sediment: under-equilibration in thicker polymers -7,5-12,5-17,5 Acenaphthylene Acenaphthene Fluorene Phenanthrene C1-Phen (5) C2-Phen (10) C3-Phen (12) Anthracene Fluoranthene C1-Fluoranth (5) Pyrene -22,5-27,5-32,5 Benzo[c]phenanthrene Benzo[a]anthracene Chrysene C1-Chrysene (1) Benzo[b+k+j]fluoranthene Benzo[a]fluoranthene Benzo[e]pyrene Benzo[a]pyrene Perylene Indeno[1,2,3cd]pyrene Dibenzo[ah]anthracene Benzo[ghi]perylene

15 t C free (ng/l) 0 water sediment S 356 µm height (cm) Acenaphthylene Acenaphthene Fluorene Phenanthrene Anthracene height (cm) Fluoranthene Pyrene Chrysene Benzo[a]anthracene water sediment Acenaphthylene Acenaphthene 200 height (cm) PE 51 µm PE 26 µm -10 water sediment Perylene Benzo[a]pyrene Benzo[b+k+j]fluoranthene Dibenzo[ah]anthracene Fluorene Phenanthrene Anthracene Indeno[1,2,3cd]pyrene Benzo[ghi]perylene C free (ng/l) 0 12,5 7,5 2,5-2,5-7,5-12,5-17,5-22,5-27,5 Fluoranthene Pyrene Chrysene -32,5 Benzo[a]anthracene Arp et al. 2011, ET&C

16 Air passive sampling silicone coated baking paper ultrathin silicone film (20 µm)

17 Conclusions & Perspective Passive sampling using polymers of multiple thickesses provides a very robust way of assessing the equilibration status. Parallel deployment of different calibrated polymers (e.g. PE and PDMS) allows cross-validation of measurements. Passive air sampling with ultrathin silicone is promising. Overall conclusion: Polymer-based exposure assessment could simplify both laboratory and regulatory work load.

18 Acknowledgements Norwegian Research Council (Grant /F20 project «FANTOM» Crew of Trygve Braarud

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20 Polyethylene and silicone passive samplers D silicone 100 x D PE! Rusina et al. 2010, Journal of Appl Pol Sci vol. 116