The Status of official standard

Transcription

1 Twinning Bulgaria Italia Training 3.3 Simitli February 2009 The Status of official standard methods with respect to the WFD requirements e e Stefano POLESELLO CNR-IRSA, Water Research Institute, Brugherio polesello@irsa. cnr.it

2 Which methods for PS monitoring? Directive 2000/60/EC Annex V, paragraph the provision of chemical data by MS shall be ensured by analytical methods that conform to relevant international or national standards or to other national or international standards or alternatively by analytical methods that are not standardised but provide data of equivalent or better scientific quality and comparability than standard analytical methods

3 Advantages and Disadvantages of standardised methods Advantages Standards are validated methods Broad acceptance within member bodies Must be transferred to national standards Standards are obliging Disadvantages Standardisation takes much time Standards always include the compromise among experts Standards do not always represent the state of the art No methods for biota and sediment (only for soil)

4 Do standard methods answer to WFD requirements? LOQ = 1/3 EQS? Whole water analysis? SPM? Are validated for the WFD matrices? Are CRM and interlab trials available?

5 Table of existing standard methods for priority substances in water

6 Pi Priority it Substance Alachlor Anthracene Atrazine Benzene Brominated diphenylethers Bis(pentabromophenyl)ether Diphenyl ether, octabromo derivate Diphenyl ether, pentabromo derivate

7 Available standard method (Ref.) Standard Year Principle ISO Jan-95 TLC, AMD-Technique US EPA 505 Jl91 Jul-91 GC/ECD (MS for conf.) ISO 17993: 2002 or see PAH s US EPA 8100 GC/FID EN ISO Nov-97 HPLC/UV EN ISO 10695: 2000 Nov-00 GC/NPD (MS for conf.) ISO Jan-95 TLC, AMD-Technique US EPA 505 Jul-91 GC/ECD (MS for conf.) DIN May-91 Headspace-GC/FID Draft ISO Sep-01 Purge/Trap + Therm. Desorp. ISO Sep-97 Headspace-GC/FID ISO WD Mar-02 GC/MS ISO WD Mar-02 GC/MS ISO WD Mar-02 GC/MS ISO WD Mar-02 GC/MS

8 Scope of method Proposed Range of Application 1 Matrix 50 ng/l Water 0,5-40 µg/l Water (D,G,S) 0,01 µg/l or 0,01 µg/l Water ca. 0,1 µg/l Water [D,G] 50 ng/l Water [D,G,S,W] 50 ng/l Water 3-50 µg/l Water [D,G,S] 5µg/l Water [D,G,S,W] 10 ng/l µg/l Water [D,G,S,W] 2 µg/l Water [D,G,S,W] µg/kg Sludge, Sediment µg/kg Sludge, Sediment µg/kg Sludge, Sediment µg/kg Sludge, Sediment

9 General ring trial data Conc. 3 S R 3 n.a. n.a. n.a. n.a. 0,03 µg/l [D] 17% 0,1-425 µg/l [D,S,W] 0,15-0,34 µg/l [D,G] % 0,12 µg/l [D] 36% 0,13 µg/l [S] 38% 5 µg/l [D,G] 7-11% 3,4-75 µg/l [D,S,W] % 200 ng/l [D,S] % 4-95 µg/l [D,S,W] 7-17% n.a. n.a. n.a. n.a. n.a. n.a. n.a. n.a.

10 Specific ring trial data for surface water Lowest conc. 3 S R 3 Application range 2 0,13 µg/l 38% 0.13 µg/l ca. 5,9 µg/l 16-29% 5,9 µg/l 0.2 µg/l 15% 0.2 µg/l 6 µg/l 16% 6 µg/l

11 Proposals for Quality standards for PS of the WFD AA-QS 7 for inland (In) & AA-QS 7 for coastal (Co) & transitional (Tr) waters territorial (Te) waters MAC-QS µg/l n.a µg/l µg/l µg/l 0.01 µg/l 0.34 µg/l 0.34 µg/l 2 µg/l 16 µg/l* 1.6 µg/l* 49 µg/l n.a. n.a. not required 33.8 µg/l (1217 µg/kg seafood, 1513 mg/kg SPM) not required µg/l µg/l 1.4 µg/l

12 Priority Substance Available standard method (Ref.) Scope of method General ring trial data Specific data for surface water Proposals for Quality standards for PS of the WFD AA-QS 7 for Proposed Range of AA-QS 7 for inland (In) & transitional )(Tr) coastal (Co) & territorial Standard Application 1 Conc. 3 Lowest conc. 3 waters (Te) waters Alachlor ISO ng/l n.a µg/l n.a. US EPA 505 0,5-40 µg/l n.a. Anthracene ISO 17993: 2002 or 0,01 µg/l 6 0,03 µg/l [D] µg/l µg/l US EPA or 0,01 µg/l 0,1-425 µg/l [D,S,W] Atrazine EN ISO ca. 0,1 µg/l 0,15-0,34 µg/l [D,G] 0.34 µg/l 0.34 µg/l EN ISO 10695: ng/l 0,12 µg/l [D] ISO ng/l 0,13 µg/l [S] 0,13 µg/l US EPA µg/l 5 µg/l [D,G] Benzene DIN µg/l 3,4-75 µg/l [D,S,W] ca. 5,9 µg/l 16 µg/l* 1.6 µg/l* Draft ISO ng/l µg/l 200 ng/l [D,S] 0.2 µg/l ISO µg/l 4-95 µg/l [D,S,W] 6 µg/l Brominated diphenylethers ISO WD µg/kg na n.a. Bis(pentabromophenyl)ether ISO WD C µg/kg chloroalkanes n.a. n.a. n.a. Diphenyl ether, octabromo deri ISO WD µg/kg n.a. g/l (1217 µg/kg seafood, 1513 mg/kg Diphenyl ether, pentabromo ISO WD µg/kg n.a µg/l µg/l Cadmium and its compound EN ISO ,3-3µg/l 0,91-16,2 µg/l [W, Dist.] 008µg/l 0.08 na n.a. DIN ,1 µg/l - 50 mg/l 0,81-3,55 µg/l [D,S] 0,81 µg/l ISO/DIS ,5 µg/l 5,75 µg/l [S] 5,75 µg/l EN ISO ,01 mg/l 100 µg/l [Std.] ISO DIS ,4-4 µg/l n.a. C10-13-chloroalkanes no Standard avail µg/l 0.1 µg/l Chlorfenvinphos DIN EN ,01-1 µg/l ng/l [W,S,G] 0,081 µg/l 0.01 µg/l 0.01 µg/l ISO ng/l n.a. Chlorpyrifos (-ethyl, -methyl) DIN EN ,01-1 µg/l n.a µg/l µg/l

13 Internal Waters: LOQ/ EQS For 21 on 31 substances methods are enough sensitive (LOQ/ EQS < 1) For 5 on 31 substances Factor 1-2 For 3 on 31 substances Factor For 2 on 31 substances Factor > 3.5 Chlorpyrifos (-ethyl, -methyl) Factor 22 Tributhyltin compounds Factor 100

14 Marine waters: LOQ/ EQS For 19 on 31 substances methods are enough sensitive (LOQ/ EQS < 1) For 3 on 31 substances Factor 1-2 For 4 on 31 substances Factor For 4 on 31 substances Factor > 3.5 γ-hch Factor 5 Benzo[K]fluoranthene Factor 18.5 Chlorpyrifos (-ethyl, -methyl)factor 22 Tributhyltin compounds Factor 100

15 Conclusions Standard methods exist for 32 on 33 substances or substance groups. No methods for chloroalkanes C10-C13 C13 Some methods do not meet minimum Some methods do not meet minimum performance criteria on EQS

16 CEN-ISO Methods

17 CEN-ISO Methods No. Principle Example (PS No.) 1 Atomic spectrometry t 2 a b c d 3 - AAS, AFS, ICP-OES, ICP-MS Cd / Pb / Hg / Ni Gaschromatography - ECD - headspace or purge and trap - liquid/liquid extraction - MS HPLC 1 / 3 / 8 / 9 / 17 / 27 4/10/11/32 / 11 / 14 / 16 / 18 / 26 / a - UV detection 13 / 19 / 29 / 33 b - fluorescence detection 2 / 15 / 22 / 28

18 Matrix Requirements from EQS Daughter Directive and QA/QC Directive key point 1 Whole water, SPM, sediment, biota Limit of quantification (LOQ) key point 2 equal or below a value of 0.3 of the relevant quality standards (EQS) LOQ versus Lower Limit of Application (LLOA) LOQ = lab specific performance value LLOA = method specific performance value Relative Target Uncertainty key point 3 a relative target uncertainty of 50% measured at the level of the relevant EQS

19 State of the Art of standardised analytical methods Lack of sensitivity of some methods (LLOA) and/or LOQ too high Statements in the standards Practical experience in many labs Published LOQs and U are sometimes Too optimistic (determined in ultraclean sample) Too pessimistic (better with modern equipment) In any case they are lab specific Lack of reliable data on Measurement Uncertainty (U) There is a need to assess realistic LOQ and U values but mainly in cases of doubts In labs from different MS e.g. by in house tests t or by ring tests t

20 Priority Substance Standard Principle inland waters Status Alachlor 1) EN ISO 6468:1996 GC/ECD C C Anthracene ISO 17993: 2002 HPLC/Fluo A A Atrazine EN ISO 11369:1997 HPLC/UV A A other waters EN ISO 10695: 2000 GC/NPD (MS for conf.) A A Benzene EN ISO 15680:2003 Purge/Trap + Therm. Desorp. A A ISO :1997 Headspace-GC/FID A A Cadmium and its compounds ISO :2003 ICP-MS B B Chlorfenvinphos EN 12918:1999 GC A A Chlorpyrifos (-ethyl, -methyl) EN 12918:1999 GC A A 1,2-Dichloroethane EN ISO 10301:1997 GC or Headspace-GC B B EN ISO 15680:2003 Purge/Trap + Therm. Desorp. A A Dichloromethane EN ISO 10301:1997 GC or Headspace-GC-ECD or other A A EN ISO 15680:2003 Purge/Trap + Therm. Desorp. A A Di(2-ethylhexyl)phthalate (DEHP) 2) ISO 18856:2004 GC/MS C C Diuron EN ISO 11369:1997 HPLC/UV A A Fluoranthene ISO 17993: 2002 HPLC/Fluo A A Hexachlorobutadiene 1) EN ISO 10301:1997 GC or Headspace-GC-ECD or other A A EN ISO 15680:2003 Purge/Trap + Therm. Desorp. A A EN ISO 6468:1996 GC/ECD C C Hexachlorocyclohexane EN ISO 6468:1996 GC/ECD C D Isoproturon EN ISO 11369:1997 HPLC/UV A A Lead and its compounds ISO :2003 ICP-MS A A ISO 15586:2003 ET-AAS B B Mercury and its compounds EN 12338:1998 CV-AAS with Amalgamation A A EN 13506:2001 Atomic fluor. spectrometry A A Naphthalene ISO 17993: 2002 HPLC/Fluo A A EN ISO 15680:2003 Purge/Trap + Therm. Desorp. A A

21 Priority Substance Standard Principle inland waters Status other waters Nonylphenols 3) ISO :2005 GC/MS C C Octylphenol (4-(1,1,3,3)- Tetramethylbutylphenol ISO :2005 GC/MS A D Pentachlorophenol EN 12673:1998 GC/ECD/MS after Deriv. A A Benzo(a)pyrene ISO 17993: 2002 HPLC/Fluo C C Benzo(b)fluoranthene 4) ISO 17993: 2002 HPLC/Fluo C C Benzo(k)fluoranthene 4) ISO 17993: 2002 HPLC/Fluo C C Simazine EN ISO 11369:1997 HPLC/UV A A EN ISO 10695: 2000 GC/MS or GC/NPD A A Trichlorobenzenes EN ISO 6468:1996 GC/ECD A A EN ISO 15680:2003 Purge/Trap + Therm. Desorp. A A Trichloromethane EN ISO 10301:1997 GC or Headspace-GC-ECD or other A A EN ISO 15680:2003 Purge/Trap + Therm. Desorp. A A Trifluralin EN ISO 10695: 2000 GC/MS or GC/ECD or GC/NPD C C DDT (4 Isomers) 5) EN ISO 6468:1996 GC/ECD C C Tetrachloroethene th EN ISO 10301: GC or Headspace-GC-ECD or other A A EN ISO 15680:2003 Purge/Trap + Therm. Desorp. A A Trichloroethene EN ISO 10301:1997 GC or Headspace-GC-ECD or other A A EN ISO 15680:2003 Purge/Trap + Therm Desorp A A Purge/Trap Therm. Desorp. Trichloromethane EN ISO 10301:1997 GC or Headspace-GC-ECD or other A A EN ISO 15680:2003 Purge/Trap + Therm. Desorp. A A

22 Summary (41 substances) 1 st 1 st st cat.: Everything is OK for about 10 substances 2 nd nd cat.: Lack of data for LOQ, U, or SPM at the time being but high probability that collected data will be OK for about 20 substances it is likely that for about 30 substances we can show in due course that they are fit for purpose

23 Summary (41 substances) 3 rd cat.: Existing standards are not suitable: (there is at tl least t1 of f3 criteria i not tok OK: LOQ, U, SPM) Problems with compliance checking for all waters TBT PAHs (6-ring ring-pah) Triflualin Problems mainly for marine waters HCH (4 relevant isomers) Octylphenol Endosulfan (a+b) Pentachlorobenzene Aldrin, Dieldrin, Eldrin, Isodrin 4 th cat.: Standardised method does not exist for water: C10-13-chloroalkanes (SCCP) Pentabromodiphenylether th (PDBE) (ISO: only for sediment)

24 Further open issue for standardised analytical methods Lack of representativeness of the Validation trials in the existing standards Matrix of tested waters not suitable Concentration range much above EQS values No or not clear statements on the suitability of the methods for whole water samples Water with remarkable SPM content