CMA on-site 1 October 2006 River Po Ferrara, Italy

Transcription

1 CMA on-site 1 October 2006 River Po Ferrara, Italy

2 CMA on-site 1: Comparison of monitoring methods on-site among few selected laboratories Comparison of River water samples (whole procedure including sampling) River water extract (measurement with real sample matrix) Standard solutions (instrumental measurement only)

3 CMA on-site 1 October 2006 Invited Participants: UBA, Austria IRSA, Italy BFG, Germany IWP, Bulgaria RIZA, Netherlands DMU, Denmark CSIC, Spain

4 Selected (challenging) organic WFD priority substances Target Compounds PBDE NP PAH Polycyclic Aromatic Hydrocarbons Polybrominated Diphenylethers Nonylphenols Octylphenol Sampling and analysis according to current WFD chemical guidance draft document and WFD EQS proposal OP

5 Sampling plan scheme for the CMA on-site exercise Time Ca. 15 min 9:30 10:00 10:30 11:00 11:30 12:00 12:30 13:00 13:30 14:00 14:30 15:00 15:30 In-situ Probe ph, cond., temperature SPM gravimetric PAH/PBDE homogeneity sampling Alkylphenols homogeneity sampling Alkylphenol sampling PAH/PBDE sampling Large volume sampling

6 Homogeneity of river water

7 Suspended Particulate Matter [mg/l] 60.0 Variability 11:00-11:30 = 8 % Variability 9:30-15:00 = 18 % :36 10:48 12:00 13:12 14:24 15:36 Sampling time Confidence interval for SPM determination < ± 5%

8 Sum of WFD PBDE [ng/l] Variability 11:00-11:30 = 11% Variability 9:30-15:00 = 31 % 9:36 10:48 12:00 13:12 14:24 15:36 Sampling time Confidence interval for for PBDE determination < ± 20 %.

9 Applied methodologies: Grab sampling

10 Applied methodologies: Centrifugation, Filtration, Adsorption

11 [ng/ml] WFD PAH calibration standard sum Standard CMA01 CMA02 CMA03 CMA04 CMA05 CMA06

12 WFD PAH in calibration standard 140 Standard CMA01 CMA02 CMA03 CMA04 CMA05 CMA [ng/ml] Anthracene Fluoranthene Benzo(a)pyrene Benzo(b+j+k)fluoranthene Benzo(g,h,i)perylene Indeno(1,2,3-cd)pyrene 0

13 WFD PAH in calibration standard 140 Standard CMA01 CMA02 CMA03 CMA04 CMA05 CMA [ng/ml] Anthracene Fluoranthene Benzo(a)pyrene Benzo(b+j+k)fluoranthene Benzo(g,h,i)perylene Indeno(1,2,3-cd)pyrene 0

14 Indeno(1,2,3-cd)pyrene WFD PAH in river water extract* CMA00 CMA02 CMA03 CMA04 CMA05 CMA [ng/ml] Anthracene Fluoranthene Benzo(a)pyrene Benzo(b+j+k)fluoranthene Benzo(g,h,i)perylene *Homogenised extract of SPM from 366 L river water

15 Fluoranthene Benzo(a)pyrene Benzo(b+j+k)fluoranthene Benzo(g,h,i)perylene Indeno(1,2,3-cd)pyrene Anthracene WFD PAH in river water 89 * CMA00 CMA01 CMA02 CMA03 CMA04 CMA05 CMA06 CMA07 value below LOQ * Average from 5 different methods [ng/l]

16 WFD PBDE in calibration standard [ng/ml] Standard CMA03 CMA04 CMA05 CMA06 BDE-28 BDE-47 BDE-99 BDE-100 BDE-153 BDE-154

17 WFD PBDE in river water extract* [ng/ml] data below LOQ CMA00 CMA03 CMA04 CMA05 CMA06 BDE-28 BDE-47 BDE-99 BDE-100 BDE-153 BDE-154 *Homogenised extract of SPM from 366 L river water

18 WFD PBDE in river water [ng/l] * CMA00 CMA03 CMA04 CMA05 CMA BDE-28 BDE-47 BDE-99 BDE-100 BDE-153 BDE-154 * CMA00 Average from 5 different methods

19 Main Conclusions: Environmental concentrations of PAH, PBDE and NP can be analysed in surface waters at concentrations taking into account the proposed EQS values and performance criteria. Very much differing sampling and analytical methodologies are currently in use within Member States Currently only few among the invited laboratories were able to deliver results at the required concentration levels Analysis of real water samples appear more variable than standards or homogenised extracts

20 In vicinity to the proposed EQS concentration levels high data quality is of importance for compliance checking Blank values in analytical procedures are of crucial importance, as analytical problems can lead also to an overestimation of pollutant content The partitioning of PBDE into the dissolved fraction, even of rather hydrophobic substances is significant, in particular in waters with a low SPM content Lowest limits of quantification have been reached by collecting SPM with a flow-through centrifuge Time integrating sampling methods would improve the reporting of annual average values

21 CMA on-site 1 report EU Report available at: /EUR_ /EUR_22922.pdf