Introduction to Passive Sampling

Transcription

1 Introduction to Passive Sampling Foppe Smedes Deltares, Utrecht, The Netherlands REETOX, Masaryk University, Brno zech Republic Linking Environmental Quality Standards and Passive sampling NORMAN expert meeting July, 2013,

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3 Pollution level in aqueous systems uptake cap. (A Sed =K Sed, W S W ) Pollution degree hemical Activity Sed Sediment SPM DO Free Dis. Air Biota Lipid 1 kg In formula: A Sed Sed = A SPM SPM = A DO DO = S W W = P P 0 = S Lipid Lipid

4 Pollution level in aqueous systems uptake cap. (A Sed =K Sed, W S W ) hemical activity Sediment SPM DO Free Dis. Air Biota Lipid Reference fase In formula: Sed DO SPM W Lipid = = = = =? Sed A? SPM A? DO SW P0 S? Lipid A P = S REF REF K Ref-W = S Ref SW = Ref W

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6 What s on the program Different passive samplers Procedures, material and methods Working principles Parameters needed Polar samplers

7 Passive sampler types Macro samplers extract and multiple analyses semipermeable membrane devices SPMD single-phase strip samplers low-density polyethylene (LDPE) polydimethylsiloxane (PDMS, silicone rubber) polyoxymethylene (POM) 18-based disk samplers (hematcher, a.o. (Polar compounds: POIS, 18...) (ceramic dosimeter) Micro passive samplers all sorbed is injected - one shot solid-phase microextraction (SPME) stir bar sorptive extraction (SBSE) rod samplers (MESO)

8 Deployment of SR and SPMD

9 Ground water

10 After exposure Foto by IOEV, Spanish Oceanographic Inst. Vigo, Spain

11 leaning sheets after recovery leaning samplers in the lab Better clean samplers in the field with local water and scourer During transport and storage redistribution could occur

12 Processing of passive samplers: SPMD Sealed in a can or glass jar Transport to Lab Extract Discard/ re-use Exterior cleaning in field Dialytic or soxhlet extraction leanup Sampler - Exposure Pre-clean spike G/MS - analysis Instrumental analysis

13 What to do with the data First need to understand the uptake

14 w Pasivesampler K / pw p When equilibrium is attained Passive sampler Surface water w w = p /K pw V w = infinitive Sampling rate R s - V p =m p K pw

15 Uptake process from water Water Boundary layer controlled Passive sampler Boundary layer Bulk water Relative conc. p /S p Diffussion W /S W p K pw D δ p D w δ w mass transfer coefficients

16 w Pasivesampler K / pw p Uptake process by a passive sampler Passive sampler Surface water w w = p /K pw V w = infinitive Sampling rate R s - V p =m p K pw

17 w Pasivesampler K / pw p Intermediate situation Passive sampler Surface water w w = p /K pw V w = infinitive Sampling rate R s - V p =m p K pw

18 How to estimate sampling rate (R s ) Release and uptake process can be mirrored Measure release of performance reference compounds (PRs) added prior to exposure

19 w Pasivesampler K / pw p Performanc reference compounds (PR) release Passive sampler Surface water w V w = infinitive Sampling rate R s - V p =m p K pw

20 Sampling rate by PRs the exchange is isotropic? Fluorene D10-Fluorene Fluoranthene D10-Fluoranthene Days Days 1.0 Uptake 1.0 Benzo(a)Pyrene D12-Benzo(e)Pyrene hrysene D12-hrysene Dissipation Days Days

21 Release of PRs with time Days deployment fraction PR retained log(k pw M 0.47 ) Data from ELIPSE project

22 Required for calculation w reference Sampler-water partition coefficient (PRs and targets) [1] Sampling rate modeled with R s =F / M 0.47 [2] Measured PR dissipation f exp =N t /N 0 fitted with f calc = e K pw F M t 0.47 m adjustable Variable, different PRs using non-linear regression fit of f exp and f calc [3] No membrane control on uptake [4] [1] Smedes et al. EST 2009 [2] Rusina et al EST 2010 [3] Booij and Smedes EST 2010 [4] Rusina et al hemosphere 2007

23 A lot of parameters needed! is that worth while?

24 Spatial distribution for PB 153 in mussels and water 50 µg/kg mussel (dry weight) 25 pg/l freely dissolved Rhine Meuse Scheldt Where source mussels were collected Start content 17 µg/kg Scheldt

25 Adsorption passive samplers used for passive sampling of polar compounds compounds well soluble in water, 1. show little absorbtion in polymers 2. usually present at higher concentrations than hydrophobic compounds higher solubility implies more possibility for fluctuations of water concentration integrative sampling needed

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27 Additional uptake through flow - POIS Flow

28 Samplers for polar compounds uptake shows the presence of substance not easy transformed to accurate w no clear uptake model yet Sampling rates in lab ~ L/d

29 Thank you for your attention Linking Environmental Quality Standards and Passive sampling NORMAN expert meeting July, 2013,

30 ontineous flow integrative samples (FIS) apable of sampling both dissolved and particulate fraction.

31 Working principles - calibration Uptake process Equilibrium or linear uptake Parameters required

32 K pw determination by cosolvent method Silicone rubber 7 6 PB153 BAP PB004 FLE 5 4 Glass bottle 10 L Glass bottle 0.25 L Molfraction methanol logk pm decreases oncentration of analyte Exposure volume Final concentration in extract constant Log K pm [1] Smedes et al. EST 2009 x methanol (Mol/Mol)

33 Material properties diffusion of target compounds -9 M (g mol -1 ) SR D in water log D (m 2 s -1 ) PAHs D from Hofmans relation LDPE PBs Silicone rubber LDPE -14 PAHs PBs [1] Rusina et al, 2010, Appl Polym Sci POM

34 Different stages of the uptake process N t amount on the sampler after t days exposure w free dissolved concentration in water m p mass sampler R s sampling rate p conc. in de sampler N t = K pw w m (= N max ) p K = pw p w absorbed amount - N t Equilibrium Intermediate linear uptake phase N t = m K p pw N t R s w t w w (1 e Rs t m K p pw ) time t

35 Uptake process from water Membrane controlled Passive sampler Water Boundary layer Non stagnant water Relative conc. p /S p Diffussion W /S W p K pw D δ p D w δ w

36 Equilibrium versus logk pw for different time periods 1 equilbrium 0.1 2xd 10xd 80xd 200xd 2000xd MatevanevenwichtDegree of Log K pw orresponding V p in L for a 10g sampler

37 Relation of Rs with hydrophobicity Several theoretical relations for D w Hayduk& Laudie Sutherland-Einstein Worch (relative scale) K ow Booij et al 2003, K ow Wilke & hang Schwarzenbachet al Rusina et al, 2010, M log R s Membrane control Empirical polynomial SPMD Huckinset al 2006 Empirical polynomial hemcatcher Vrana et al log K ow

38 Examples of fiting 2001 Autumn, Station 1 Wadden Sea 1.0 R s 300 =10.9 (±1.0) L/d f exp -f calc 0.10 retained PR fraction retained PR fraction f exp f calc log(k log(k pw /M 0.47 pw /M 0.47 ) ) Winter, Station 1 Wadden Sea R s 300 =22.6 (±1.8) L/d f exp f calc log(k pw /M 0.47 ) f exp -f calc log(k pw /M 0.47 )

39 Biofouled! fraction PR retained f-exp f-calc R s 300 =2.2 (±0.2) log(k pw /M )