Monitoring of metals in surface waters: an in situ intercomparison exercise on passive samplers

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Monitoring of metals in surface waters: an in situ intercomparison exercise on passive samplers

A. Dabrin, J.L. Gonzalez, J.P. Ghestem, E. Uher, Cecile Miege, Marina Coquery, I.J. Allan, M. Schintu, J. Balaam, E. Peinerud, et al.

To cite this version:

A. Dabrin, J.L. Gonzalez, J.P. Ghestem, E. Uher, Cecile Miege, et al.. Monitoring of metals in surface waters: an in situ intercomparison exercise on passive samplers. 6th International Passive Sampling Workshop IPSW, Jun 2013, Bordeaux, France. pp.1, 2013. �hal-02599289�

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Monitoring of metals in surface waters:

an in situ intercomparison exercise on passive samplers

A. Dabrin^1*, J-L. Gonzalez², J-P. Ghestem³, E. Uher⁴, C. Miège¹, M. Coquery¹ I.J Allan⁵, M. Schintu⁶, J. Balaam⁷, E. Peinerud⁸, N Montero⁹, N. Chhim¹⁰

1*IRSTEA, UR MALY, 5 rue de la Doua, CS700077, F-69626 Villeurbanne Cedex, France, ² Ifremer, F- 83507,La Seyne/Mer, France, ³BRGM, F-45060, Orléans, France, ⁴Irstea, UR HBAN, F-92163, Antony, France.

5NIVA, Oslo, Norway, ⁶Università degli Studi di Cagliari, Italy, ⁷Cefas, Centre for the Environment Fisheries and Aquaculture Science, Lowestoft, United Kingdom, ⁸ALS Scandinavia, Sweden, ⁹AZTi- Tecnalia, Marine Research Division, 20110 Pasaia, Spain, ¹⁰EDF R&D, LNHE, Moret-sur-Loing, France

*: corresponding author ([email protected])

Objective of the AQUAREF intercomparison passive sampling exercise 1

Description of the trials 2

Significant Results 3

Coastal waters

Thau Lagoon (Hérault)

River Waters

Rhône River: Ternay site

● Data dispersion of passive samplers

● Context: In the context of the Marine Strategy Framework Directive (MSFD) and the Water Framework Directive (WFD), monitoring of marine waters and freshwaters quality became a crucial point. Thus, there is a need to apply innovative sampling tools in surface waters such as passive samplers, taking into account temporal and spatial aspects, with a limited cost and easy to use by non-expert routine laboratories.

● 2 sampling sites ● 10 European expert laboratories

5 FR, ES, UK, SWE, NO, IT

(10 at Ternay site, 6 at Thau site)

● Lab usual tools & protocols - 3 types of passive samplers

DGT OP: Diffusive Gradient in Thin films (Chelex-100, « open pores » gel DGT RP: Chelex-100, « restrictive pores » gel

Chemcatcher^® (Empore chelating disc)

- Analytical procedures

Elution (HNO₃ 1M), ICP-MS or GF/AAS

- Data treatment

Diffusion coefficients from literature

● Common constraints

- Exposure of passive samplers

Exposure in triplicate (7 days) Field blank

- Analytical control (QC)

Analysis of a reference solution (8 metals at 1 µg/L)

- Target metals

Priority substances (WFD): Cd, Pb and Ni

Other metals (including 3 of the good ecological status):

Cr, Zn, Cu, Mn and Co

● Comparison of passive sampling results from various tools and laboratories

● Comparison of TWAC vs Spot sampling

● Field and lab blanks

Metals Robust mean Robust mean LQ

x* ± SD RSD n x* ± SD RSD n Water

(µg/L) % (µg/L) % µg/L

Cd 0.005 ± 0.003 58 12 0.027 ± 0.025 92 7 0.010 Cr 0.076 ± 0.070 93 11 0.036 ± 0.029 80 7 0.050 Cu 0.367 ± 0.153 42 13 0.233 ± 0.1089 47 7 0.050 Mn 3.47 ± 0.99 28 11 7.48 ± 2.646 35 7 0.100 Ni 0.392 ± 0.139 35 13 0.261 ± 0.1265 48 7 0.050 Pb 0.063 ± 0.070 112 12 0.021 ± 0.012 58 6 0.010 Zn 1.40 ± 1.10 79 10 3.15 ± 3.13 99 5 0.500

Passive sampler data

Ternay site Thau site

Robust mean

x* ± SD RSD n

(µg/L) %

0.09 ± 0.08 89 27 1.73 ± 1.57 91 36 4.15 ± 1.66 40 42 154 ± 17 11 47 1.85 ± 1.40 75 32 1.20 ± 0.83 69 31 12.3 ± 2.8 23 39 SWIFT - WFD proficiency Testing

Exercise (2006)

Ternay site

TWAC (mean of all PSs)

Dissolved concentrations (< 0.45 µm)

(mean of 3 spot sampling during field exposure)

2 3 4

Cd*100 Cr*10 Co*10 Cu Mn/10 Ni Pb Zn

x* ± S _R

0.0053 ± 0.0031 µg/L

0.013 ± 0.002 µg/L (spot sampling)

10138 - DGT RP 10140 - DGT RP

0 0.01 0.02 0.03 0.04 0.05 0.06 0.07 0.08 0.09 10103 - DGT

10111 -DGT 10125 - DGT 10123 -DGT 10127 - DGT 10126 - Chemcatcher 10132 - DGT

10116 - DGT 10118 - DGT 10124 -DGT

LQ

Cd

Field blanks Sample

● PSs allow to decrease limit of quantification (LQ).

● Comparison with a classical proficiency testing exercise, only taking into account analytical procedure, show a similar dispersion for Cd, Cr and Cu, a lower dispersion for Ni, and a higher dispersion of PSs data for Pb and Zn.

● The reproducibility is very satisfying considering the different tools and analytical procedures. Since analytical variability was low in this exercise (from 8 to 25%), the dispersion was mainly due to PS deployment step.

● TWAC were systematically lower or similar to total dissolved concentrations obtained after spot sampling

● For example, dissolved Mn was totally sampled, while only 35% of dissolved Cu was sampled by PSs.

1

0

Concentration (µg/L)

x* ± S _R

0.063 ± 0.070 µg/L

0 0.05 0.1 0.15 0.2 0.25 0.3 0.35 0.4

10126 - Chemcatcher

10138 – DGT RP

10140 – DGT RP 10111 - DGT 10125 - DGT 10132 - DGT 10103 - DGT 10127 - DGT 10118 - DGT 10123 - DGT 10116 - DGT 10128 - DGT

LQ

Pb

x* ± S _R

0.392 ± 0.139 µg/L

µg/L

0 0,2 0,4 0,6 0,8 1 1,2

10138 - DGT RP 10126 - Chemcatcher 10111 - DGT 10103 - DGT

10132 - DGT 10127 - DGT 10124 - DGT 10125 - DGT

10118 - DGT 10128 - DGT 10123 - DGT 10116 - DGT 10140 –DGT RP

Ni

LQ

Aberrant values

Dispersion (Cochran test) Mean (Grubbs test)

QC

PSs data

Ternay site

● For Cd, results are similar except for 3 labs which showed high within-laboratory variability for PSs data. No significant differences between DGT with open or restrictive pores were found.

● Pb presents high variability with 6 labs out of 10 in where aberrant values for CQ or PSs were obtained.

● For Ni, results of PSs are homogeneous (except one outlier) and no differences between Chemcatcher, DGT OP and DGT RP results were found.

Ternay site

● Mass of Co, Cu, Mn, and Ni in field blanks are relatively low compared with the mass in tools deployed in situ, which is not the case for Cd, Cr, Pb and Zn

Cd Cr

Cu Mn Ni

Pb Zn

0 5 10 15 20 25

10103 - DGT 10111 - DGT 10116 - DGT 10118 - DGT 10123 - DGT 10124 - DGT 10125 - DGT 10126 - Chemc.

10127 - DGT 10128 - DGT 10132 - DGT 10138 DGT - RP 10140 DGT - RP

0 50 100 150 200 250 300 0 1000 2000 0 100 200 300

0 5 10 15 20 25 30 35 40 0 2000 4000

0 2 4 6 8 10 12 14 16

Co

0 2 4 6 8 10 12 14 16

10127 - DGT 10128 - DGT 10132 - DGT 10138 - DGT- RP 10140 DGT - RP

10127 - DGT 10128 - DGT 10132 - DGT 10138 - DGT - RP 10140 DGT - RP

Mean = 17% Mean = 1%

Mean = 24%

Mean = 17%

ng of metal in field blank ng of metal in tool deployed in situ

0 2 4 6 8 10

ng/tool

Cd

Laboratories

Acid blank DGT lab-blank DGT field-blank

Mean = 72% Mean = 70%

Mean = 290% Mean =110%

● For example, high Cd contents in DGT field blanks seem related to a contamination from the DGT resin (DGT lab-blank)

For more information: Miège et al, Trends Anal. Chem., 2012,36, 128-143

www.aquaref.fr/reunion-de-restitution-essai-interlaboratoire-echantillonneurs-integratifs

● Aim : To assess the relevance of passive samplers for the monitoring of metals in surface freshwaters and coastal waters, an in-situ intercomparison passive sampling exercise was realised in 2010. The aim of this study was to assess interlaboratory variability, at each step of the exercise leading to a “dissolved-labile”

metal Time Weighted Average Concentration (TWAC).

x 100

RSD 58%

RSD 112%

RSD 35%