AMPS 2003AMPS Delegates:

All Member States and 10 Candidate Countries

AMPS 1 February 2002

Drafting group: Table of existing methods

EAF (4)-05/02/JRC-IES

Drafting group: Document on new analytical methods

EAF (4)-05/03/JRC-IES

AMPS 2 January 2003

Table with existing analytical methods

One page

“Task is to provide a comprehensive table, which compiles information on CEN/ISO methods including performance criteria and other information necessary for policy support “ (AMPS 1)

Basis for:

• identification/discussion of needs for development

•advice to EAF on PS

Priority Substance

Alachlor

Anthracene

Atrazine

Benzene

Brominated diphenylethersBis(pentabromophenyl)etherDiphenyl ether, octabromo derivateDiphenyl ether, pentabromo derivate

Standard Year Principle

ISO 11370 2000 Jan-95 TLC, AMD-TechniqueUS EPA 505 Jul-91 GC/ECD (MS for conf.)

ISO 17993: 2002 or see PAH´sUS EPA 8100 GC/FIDEN ISO 11369 Nov-97 HPLC/UVEN ISO 10695: 2000 Nov-00 GC/NPD (MS for conf.)ISO 11370 2000 Jan-95 TLC, AMD-TechniqueUS EPA 505 Jul-91 GC/ECD (MS for conf.)DIN 38407-9 May-91 Headspace-GC/FIDDraft ISO 15680 Sep-01 Purge/Trap + Therm. Desorp.ISO 11423-1 Sep-97 Headspace-GC/FIDISO WD 22032 Mar-02 GC/MSISO WD 22032 Mar-02 GC/MSISO WD 22032 Mar-02 GC/MSISO WD 22032 Mar-02 GC/MS

Available standard method (Ref.)

Proposed Range of

Application1 Matrix

50 ng/l Water0,5-40 µg/L Water (D,G,S) 0,01 µg/l 6

0.1 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 Water3-50 µg/L Water [D,G,S] 5 µg/l Water [D,G,S,W]

10 ng/l - 100 µg/l Water [D,G,S,W] 2 µg/l Water [D,G,S,W]

0.005 - 100 µg/kg Sludge, Sediment0.03 - 100 µg/kg Sludge, Sediment0.005 - 25 µg/kg Sludge, Sediment0.005 - 25 µg/kg Sludge, Sediment

Scope of method

Proposed Range of

Application1 Matrix

50 ng/l Water0,5-40 µg/L Water (D,G,S) 0,01 µg/l 6

0.1 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 Water3-50 µg/L Water [D,G,S] 5 µg/l Water [D,G,S,W]

10 ng/l - 100 µg/l Water [D,G,S,W] 2 µg/l Water [D,G,S,W]

0.005 - 100 µg/kg Sludge, Sediment0.03 - 100 µg/kg Sludge, Sediment0.005 - 25 µg/kg Sludge, Sediment0.005 - 25 µg/kg Sludge, Sediment

Scope of method" The range of application corresponds to the lowest and highest concentrations for which tests of precision and bias have been carried out using the system without modification...“

(ISO/TR 13530, 1997-09)

Range of Application

Proposed Range of

Application1 Matrix

50 ng/l Water0,5-40 µg/L Water (D,G,S) 0,01 µg/l 6

0.1 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 Water3-50 µg/L Water [D,G,S] 5 µg/l Water [D,G,S,W]

10 ng/l - 100 µg/l Water [D,G,S,W] 2 µg/l Water [D,G,S,W]

0.005 - 100 µg/kg Sludge, Sediment0.03 - 100 µg/kg Sludge, Sediment0.005 - 25 µg/kg Sludge, Sediment0.005 - 25 µg/kg Sludge, Sediment

Scope of methodDrinking

Ground

Surface

Waste

WATER

Sludge

Sediment

Soil

Matrix

Conc. 3 SR3

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] 11 - 16 %

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] 16 - 27 %200 ng/l [D,S] 14 - 15 %

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.

General ring trial data

Lowest conc. 3 SR3 Application range2

0,13 µg/l 38% 0.13 µg/l

ca. 5,9 µg/l 16-29% 5,9 µg/l0.2 µg/l 15% 0.2 µg/l6 µg/L 16% 6 µg/l

Specific ring trial data for surface water

Method-Applicability

Applicability in routine labs - (yes/no) or remarks

no (2), yes (2)--

yes (2)yes (1)

no (1), yes (1)no (1), yes (2)

no (1)--

no (1), yes (1)no (1), yes (1)

yes (1)no (3), yes (1)

------

Applicability in routine laboratories Method-Applicability

Applicability in routine labs - (yes/no) or remarks

no (2), yes (2)--

yes (2)yes (1)

no (1), yes (1)no (1), yes (2)

no (1)--

no (1), yes (1)no (1), yes (1)

yes (1)no (3), yes (1)

------

Standard methods being applied in a modified form were calculated as “yes”

Input from 4 countries (yes/no or remarks)

AA-QS7 for inland (In) & transitional (Tr) waters

AA-QS7 for coastal (Co) & territorial (Te) waters MAC-QS7

0.035 µg/l n.a. 1.15 µg/l

0.063 µg/l 0.0063 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 requirednot required

0.0005 µg/l 0.00018 µg/l 1.4 µg/l

Proposals for Quality standards for PS of the WFD

33.8 µg/l (1217 µg/kg seafood, 1513 mg/kg SPM)

Conclusions

Analytical standard methods for 32 of 33 compounds/compound groups are available

Method performance data do not match all EQS proposals for inland waters and marine waters

Inland Water: Lower method application range /proposed EQS

For 21 of 31 substances methods sufficiently sensitive

(lower method application range /proposed EQS < 1)

For 5 of 31 substances Factor 1- 2

For 3 of 31 substances Factor 2 – 3.5

For 2 of 31 substances Factor > 3.5

Chlorpyrifos (-ethyl, -methyl) Factor 22

Tributyltin compounds Factor 100

Marine Water: Lower method application range /proposed EQS

For 19 of 29 substances methods sufficiently sensitive

(lower method application range /proposed EQS < 1)

For 3 of 31 substances Factor 1- 2

For 4 of 31 substances Factor 2 – 3.5

For 4 of 31 substances Factor > 3.5

Chlorpyrifos (-ethyl, -methyl) Factor 22

-HCH Factor 5

Benzo[K]fluoranthene Factor 18.5

Tributyltin compounds Factor 100

Need of aquatic reference materials for QA/QC

No information on cost of monitoring:

only 2 contributions, no sampling costs

No harmonised method for chloroalkanes available

21 of 33 substances are covered by methods from 2000/2001/2002

Not all methods are up-to-date

Conclusions

Conclusions

Use of alternative methods is desired by AMPS members

The use of standard methods alone does not guarantee comparable data across Europe

Need for standard/reference methods as guidelines and for definition of analytes

Longterm need for a European proficiency testing scheme

Identification of data quality requirements necessary

Drafting group on data quality requirements

New analytical methodsStill problematic:•PBDE

•SCCP

•Alkylphenols

•Phthalate

Document should be further commented, developed and should present an overview on still remaining problems in method development for WFD PS

Need for further method development, testing and interlaboratory comparisons

Natural metal background concentrations

No harmonised method for deriving geogenic metal background concentrations in water is currently available

General agreement with proposal for metal EQS setting

Drafting group on metal background concentrations

Suspended Particulate Matter/Sediment/Biota Monitoring

MS/CC have more experience with sediment

SPM sampling not in all water types possible

Discussion on feasibility of different approaches

Need to identify different monitoring needs for different water types ?

Background documents to be provided

Future AMPS tasks

Support to review of PS list

Contact between Marine and Inland monitoring is established (ICES) and needs to be enhanced

Coverage of Mediterranean area ?

Non target methods for river basin specific contaminants

AMPS 2 Actions

Background documents on SPM/Sediment/Biota monitoring will be provided

Drafting group: Metal background concentrations

Drafting group: Data quality objectives/requirements

Additional AMPS (3) meeting in April

AMPS 2 minutes still need to be commented by members !