Intercomparison of five integrative samplers for the monitoring of indicator and dioxin-like PCBs in the laboratory and in situ (ECLIPSE project)

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Intercomparison of five integrative samplers for the monitoring of indicator and dioxin-like s in the laboratory and in situ (ECLIPSE project) R. Jacquet 1, C. Miège 1, F. Smedes 2, C. Tixier 3, J.

2 Deltares, PO Box 85467, 358AL, Utrecht, The Netherlands. 3 Ifremer, DCN-BE, rue de l Ile d Yeu, 44311 Nantes, France. 4 BRGM, 3 av. Claude Guillemin, 456 Orléans, France.

1 Intercomparison of five integrative samplers for the monitoring of indicator and dioxin-like s in the laboratory and in situ (ECLIPSE project) R. Jacquet 1, C. Miège 1, F. Smedes 2, C. Tixier 3, J. Tronczynski 3, C. Berho 4, A. Togola 4, I. Valor 5, J. Llorca 5, B. Barillon 6, P. Marchand 7, M. Coquery 1 1 Cemagref, UR MALY, 3 bis quai Chauveau, Lyon, France. 2 Deltares, PO Box 85467, 358AL, Utrecht, The Netherlands. 3 Ifremer, DCN-BE, rue de l Ile d Yeu, Nantes, France. 4 BRGM, 3 av. Claude Guillemin, 456 Orléans, France. 5 LABAQUA, c/ Dracma 16-18, Poligono Industrial Las Atalayas, 3114 Alicante, Spain. 6 Suez Environnement CIRSEE, 38 rue du Président Wilson, 7823 Le Peck, France. 7 LABERCA-ONIRIS, route de Gachet, 4437 Nantes, France. contact: cecile.miege@cemagref.fr AQUAREF Symposium, Passive Samplers and Alternative Sampling Techniques, November 24 th 211, Nantes, France

2 Presentation of the ECLIPSE project Context: Innovative sampling tools needed for the monitoring of in water Various integrative samplers available to estimate TWA concentration ECLIPSE: Integrative samplers for the monitoring of in water 3 years (29-211) 5 laboratories Objectives: Evaluation of 5 integrative samplers to monitor in water Comparison of performances: uptake kinetics, repeatability, accuracy Planning: 1 st year: simultaneous calibration of samplers in laboratory 2 nd and 3 rd year: deployment of samplers in real aquatic environments AQUAREF Symposium, November 24 th 211, Nantes, France N 2

integrative samplers to monitor in water Comparison of performances: uptake kinetics, repeatability, accuracy Planning: 1 st year: simultaneous

3 Integrative samplers studied in the ECLIPSE project Semi-permeable membrane device (SPMD) Layflat LDPE* tube containing triolein Cemagref (Lyon, France) Low-density polyethylene strip LDPE* strip Ifremer (Nantes, France) Silicone rubber PDMS* rubber Deltares (Utrecht, The Netherlands) Chemcatcher LDPE* membrane covering a C18 Empore disk BRGM (Orléans, France) Continuous-flow integrative sampler (CFIS) Small PDMS* pieces, use of pump and batteries Labaqua (Alicante, Spain) * LDPE: low-density polyethylene, PDMS: polydimethylsiloxane AQUAREF Symposium, November 24 th 211, Nantes, France N 3

Chemcatcher LDPE* membrane covering a C18 Empore disk BRGM (Orléans, France) Continuous-flow integrative sampler (CFIS) Small PDMS* pieces, use of

4 1) Simultaneous calibration of samplers in laboratory AQUAREF Symposium, November 24 th 211, Nantes, France N 4

5 Calibration experiment (July-Sept. 29) Exposure conditions: Calibration device made of stainless steel to limit adsorption of 2 L of unfiltered tap water Water velocity: about 5 cm/sec, temperature: 22.6 C (±.1 C) Exposure durations: 1, 3, 7, 14 (x3), 21, 28 (x3), 56 and 91 days Concentration of each in water of about 1 ng/l: Immersion of spiked silicone sheets [Rusina et al, 21] ind : (18), 28, 52, 11, 118, 138, 153, 18 D-L : 77, 81, 15, 114, (118), 123, 126, 156, 157, 167, 169, 189 Before exposure, samplers spiked with PRC (except CFIS) Dosing sheets and water sampled every 15 days: concentrations (, 3% < RSD < 1%) ph (, 7.5 ±.2), conductivity ( from 38 to 31 µs/cm) and DOC concentration ( from 1.5 to 4.7 mg/l) AQUAREF Symposium, November 24 th 211, Nantes, France N 5

1 C) Exposure durations: 1, 3, 7, 14 (x3), 21, 28 (x3), 56 and 91 days Concentration of each in water of about 1 ng/l: Immersion of spiked silicone sheets [Rusina et al, 21] ind : (18), 28, 52,

6 Calibration device (1/3) Stirrer engine CFIS Stainless steel tank (calibration) Polyethylene tank (water bath) AQUAREF Symposium, November 24 th 211, Nantes, France N 6

7 Calibration device (2/3) Inside the tank, 6 racks immersed: 2 racks for dosing sheets 4 racks for samplers (with 4 positions on each) Position 1: blank sampler (no PRC) Position 2: variable exposure durations Position 3: variable exposure durations Position 4: 91 days exposure Dosing sheets (source of contamination) SPMD Silicone rubbers LDPE strips Chemcatchers AQUAREF Symposium, November 24 th 211, Nantes, France N 7

durations Position 3: variable exposure durations Position 4: 91 days exposure Dosing sheets (source of

8 Calibration device (3/3) Inside the tank: dosing sheets and passive samplers Outside the tank: CFIS AQUAREF Symposium, November 24 th 211, Nantes, France N 8

9 Uptake (ng for 1cm Uptake curves of and release curves of PRC 1 S P MD 1 1 SR 35 NP RC / N,P RC,8,6,4,2 PC B PC B 29 (PRC) Uptake (ng for 1cm ) NP RC / N,P RC,8,6,4, (PR C ) ) Exposure duration (days) Exposure duration (days) NP RC / N,P RC 1,8,6,4,2 L D P E PC B (PRC) Uptake (ng for 1cm ) NP RC / N,P RC 1,8,6,4,2 C h em catch er Fluorene-d1 (PRC) Uptake (ng for 1cm ) Exposure duration (days) C F IS PC B Exposure duration (days) SPMD: transfert of and PRC stopped after 56 days, due to biofouling? After 91 days of exposure, equilibrium reached for 18, 28 and 52 in LDPE Overall good linearity of uptake curves AQUAREF Symposium, November 24 th 211, Nantes, France N Uptake (ng for 1cm ) Exposure duration (days)

N,P RC 1,8,6,4,2 C h em catch er 81 114 138 Fluorene-d1 (PRC) 8 6 4 2 2 Uptake (ng for 1cm ) 2 4 6 8 1 Exposure duration (days) C F IS PC B 81 114 138 2 4 6 Exposure duration (days) SPMD: transfert

10 Uptake (ng for 1cm 2 ) Concentration of in triplicate samplers SPMD (28 days) Silicone rubber (28 days) LDPE strip (28 days) Chemcatcher (14 days) CFIS (14 days) Repeatability of uptake: SPMD: 1% < RSD < 18% (mean = 7%) Silicone rubber: 2% < RSD < 9% (mean = 4%) LDPE strip: 1% < RSD < 25% (mean = 6%) Chemcatcher: 3% < RSD < 13% (mean = 8%) CFIS: 2% < RSD < 2% (mean = 11%) AQUAREF Symposium, November 24 th 211, Nantes, France N 1

Repeatability of uptake: SPMD: 1% < RSD < 18% (mean = 7%) Silicone rubber: 2% < RSD < 9% (mean = 4%) LDPE strip: 1% < RSD < 25%

11 R S calculated from nominal concentrations RS (L/day for 1cm 2 ) SPMD SR LDPE strip Chemcatcher CFIS concentrations in water calculated from dosing sheets N = R S.C W.t when N = f(t) is plotted, slope = R S.C W Overall trends of sampling rates: CFIS: highest rates for light but low rates for the others Silicone rubber LDPE strip SPMD CFIS Chemcatcher Silicone rubber, LDPE strip and SPMD: higher sampling rates + higher surface area most efficient samplers to decrease LOQ AQUAREF Symposium, November 24 th 211, Nantes, France N 11

C W Overall trends of sampling rates: CFIS: highest rates for light but low rates for the others Silicone rubber LDPE strip SPMD CFIS Chemcatcher Silicone

12 TWA concentrations of in water To calculate TWA concentrations, need for : Uptake models Choice criteria of PRC Low K SW Models, PRC and log K SW used Model PRC Log K SW SPMD Huckins 26 (water boundary layer - controlled uptake model), used when dissipation was between 2% and 8% empirical relationship function of log K OW [Huckins 26] SR Rusina 21 (non linear fit of R S to observed dissipation), all used with unweighted nonlinear least-squares regression [Booij 21] measured and modeled [Smedes 29] LDPE strip Huckins 26 (water boundary layer - controlled uptake model), used when dissipation was between 2% and 8% measured and modeled [Smedes 29] Chemcatcher Vrana 27 (applicable for compounds with 3.7 < log K OW < 6.8) PAH, used when dissipation was between 2% and 1% empirical relationship function of log K OW [Vrana 26] CFIS none, use of predetermined R S for ind and extrapolated R S for dl none, not required none, not required Chemcatcher results (model applied for with log K OW < 6.8): 14% < RSD < 17% (mean = 15%) TWA concentrations of up to 12 times higher than the other samplers AQUAREF Symposium, November 24 th 211, Nantes, France N 12

dissipation), all used with unweighted nonlinear least-squares regression [Booij 21] measured and modeled [Smedes 29] LDPE strip Huckins 26 (water boundary layer - controlled uptake model), used when

13 TWA concentration of in water (ng/l) TWA concentrations of in water 3 Reference concentration in water calculated from concentration in dosing sheets (PDMS): C W = C PDMS K PDMS,W SPMD SR LDPE strip CFIS Reference Ratio to reference RSD SPMD 79% - 212% (mean = 145%) 6% - 21% (mean = 13%) Silicone rubber 147% - 275% (mean = 27%) 1% - 27% (mean = 18%) LDPE strip 4% - 123% (mean = 69%) 9% - 44% (mean = 3%) CFIS 65% - 272% (mean = 146%) 5% - 15% (mean = 7%) AQUAREF Symposium, November 24 th 211, Nantes, France N 13

81 114 Ratio to reference RSD SPMD 79% - 212% (mean = 145%) 6% - 21% (mean = 13%) Silicone rubber 147% - 275% (mean = 27%) 1% - 27% (mean = 18%) LDPE

14 Conclusions about calibration Calibration experiment successfull For Chemcatcher: Literature model for hydrophobic compounds not applicable for Sampling rates determined for the 19 of ECLIPSE For CFIS: Sampling rates confirmed for indicator Sampling rates determined for dioxin-like TWA concentrations of (except Chemcatcher): Good agreement between samplers (29% < RSD < 51%) Highest difference: a factor of 4.25 for 18 between LDPE strip (.4 ng/l) and CFIS (1.7 ng/l) Ratio to reference between 48% and 272% AQUAREF Symposium, November 24 th 211, Nantes, France N 14

dioxin-like TWA concentrations of (except Chemcatcher): Good agreement between samplers (29% < RSD < 51%) Highest difference: a factor of 4.

15 2) Deployment of samplers for field campaigns AQUAREF Symposium, November 24 th 211, Nantes, France N 15

16 Field campaigns 3 field campaigns performed in: The Rhône River at Ternay (June-July 21) The Rhône River at Arles (Oct-Nov 21) The Leysse River at Bourget-du-Lac (June-July 211) Ternay Arles Bourget-du-Lac Exposure of samplers: At 1 m of depth using appropriate canisters, holders and buoys During 1, 2, 3 and 4 weeks with duplicate and/or triplicate Monitoring of water temperature, velocity, conductivity, ph, DOC, TOC and ions concentrations AQUAREF Symposium, November 24 th 211, Nantes, France N 16

using appropriate canisters, holders and buoys During 1, 2, 3 and 4 weeks with duplicate and/or triplicate Monitoring of

17 Uptake (ng/sampler) Uptake (ng/sampler) Uptake (ng/sampler) Uptake (ng/sampler) Ternay: uptake of and release of PRC NPRC/N,PRC 1,,9,8,7,6,5,4,3,2,1 SR 2 (PRC) NPRC/N,PRC 1,,9,8,7,6,5,4,3,2,1 LDPE 29 (PRC) , Exposure duration (days), Exposure duration (days) in SR in LDPE a + 21b 14a + 14b 21a + 7b a + 21b 14a + 14b 21a + 7b Sampling in the integrative phase of uptake AQUAREF Symposium, November 24 th 211, Nantes, France N 17

Exposure duration (days) 45 4 153 in SR 25 153 in LDPE 35 3 25 21 14 7 2 15 21 14 7 2 15 1 5 7 14 21 28 28 28 1 5 7 14 21 28 28 28 7a + 21b 14a + 14b 21a

18 Uptake (ng/sampler) Ternay: uptake of CFIS,12, ,8,6,4, Exposure duration (days) SPMD: analytical problems, quantification unreliable for PRC of interest (samples currently analysed with another GC apparatus) Chemcatcher: low and erratic accumulation AQUAREF Symposium, November 24 th 211, Nantes, France N 18

interest (samples currently analysed with another GC apparatus) Chemcatcher: low

19 Concentration (ng/l) TWA concentration (ng/l) TWA concentration (ng/l) Ternay: TWA concentrations of in water,5,4 SR LDPE,5,4 CFIS,3,3,2,2,1,1, , Close results for SR and LDPE: [] SR / [] LDPE < 2 RSD < 4%,25,2,15 Water samples (n=4) CFIS: [] CFIS / [] SR < 11 9% < RSD < 61%,1,5, AQUAREF Symposium, November 24 th 211, Nantes, France N 19

results for SR and LDPE: [] SR / [] LDPE < 2 RSD < 4%,25,2,15 Water samples (n=4) CFIS: [] CFIS / [] SR

20 Conclusions about field campaign Similar results for SR and LDPE strips with good repeatability Results for dioxin-like? Higher TWA concentrations measured with CFIS Longer exposure durations to increase accumulated amounts? Low and erratic uptake with Chemcatcher Probably not suitable for monitoring Problem during analysis of SPMD extracts Use of another GC equipped with two columns in parallel Results of Arles and Lac-du-Bourget campaigns? AQUAREF Symposium, November 24 th 211, Nantes, France N 2

Low and erratic uptake with Chemcatcher Probably not suitable for monitoring Problem during analysis of SPMD extracts Use of

21 Thank you for your attention AQUAREF Symposium, November 24 th 211, Nantes, France N 21

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