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F INTRODUCTION F STATE of RESEARCH on - Alkylphenols

„Pre-normative research on method development and validation for selected priority substances“ Peter Lepom, Federal Environmental Agency, Berlin AMPS-Meeting, JRC Ispra, 27 February 2002. German Federal Environmental Agency, Laboratory of Water Analysis (Section II 3.5). F INTRODUCTION

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F INTRODUCTION F STATE of RESEARCH on - Alkylphenols

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  1. „Pre-normative research on method development and validation for selected priority substances“ Peter Lepom, Federal Environmental Agency, Berlin AMPS-Meeting, JRC Ispra, 27 February 2002 German Federal Environmental Agency, Laboratory of Water Analysis (Section II 3.5) FINTRODUCTION FSTATE of RESEARCH on - Alkylphenols - Polybrominated Diphenylethers (PBDEs) - Polychloroalkanes C10 – C13 (PCAs) FCONCLUSION

  2. GENERAL CONSIDERATIONS German Federal Environmental Agency, Laboratory of Water Analysis (Section II 3.5) FIdentification of compounds for which there is a need of method development FIn case of substance groups – analysis of indicator compounds versus total content determination FWhat are the requirements with regard to sensitivity on the analytical procedures to develop? FIdentification of the most appropriate matrix for analysis and to meet the requirements of the directive

  3. ALKYLPHENOLS - METHODS German Federal Environmental Agency, Laboratory of Water Analysis (Section II 3.5) FNormal-phaseHPLC with fluorescence or UV-detection FHigh-resolution capillary gas chromatography with mass selective detection after derivatisation FHigh-resolution capillary gas chromatography with mass selective detection

  4. ALKYLPHENOLS – ISO/CD 18857-1 German Federal Environmental Agency, Laboratory of Water Analysis (Section II 3.5) Compounds:Nonylphenol, Octylphenol Range of application:0.005 to 0.2 µg/L (surface water) Extraction: Liquid-liquid extraction with toluene Clean-up (if required): Column chromatography on silica gel Detection: GC-MS in the selected ion monitoring mode (m/z=107/135) Quantification: Calibration with 4-iso-nonylphenol and 4-(1,1,3,3-tetramethylbutyl)phenol ESTD calibration of the overall procedure ISTD: 13C6-ring-labelled 4-n-nonylphenol

  5. ALKYLPHENOLS - INTERLABORATORY STUDY German Federal Environmental Agency, Laboratory of Water Analysis (Section II 3.5) FOrganised by the Bavarian Water Management Agency Munich, Germany F17 laboratories from 6 countries FThree water samples each in duplicate surface water – low level (0.005 to 0.05 µg/L) surface water – high level (0.05 to 0.2 µg/L) WTP effluent (0.1 to 25 µg/L) FCalibration standard solution FSample shipment on 25 February 2002 FData assessment according to ISO 5725-2

  6. POLYBROMINATED DIPHENYLETHERS (PBDEs) Technical mixtures German Federal Environmental Agency, Laboratory of Water Analysis (Section II 3.5) F Penta-BDE Mixture of tetra-, penta-, and hexabromodiphenylethers; BDE-47, BDE-99, BDE-100, BDE-153 and BDE-154 constitute more than 80% of the technical product FOcta-BDE Mixture of hepta-, octa- and nonabromodiphenylethers; BDE-183 can be used as indicator compound FDeca-BDE Decabromodiphenylether makes up more than 97%

  7. POLYBROMINATED DIPHENYLETHERS (PBDEs) Methods German Federal Environmental Agency, Laboratory of Water Analysis (Section II 3.5) FGas chromatography with electron capture detection (GC-ECD) FGas chromatography with atomic emission detection (GC-AED) FGas chromatography with electron impact mass spectro- metric detection at low resolution (GC-LRMS) FGas chromatography with electron impact mass spectro- metric detection at high resolution (GC-HRMS) FGas chromatography with electron capture negative ionisation mass spectrometric detection (GC-ECNI-MS)

  8. POLYBROMINATED DIPHENYLETHERS (PBDEs) GC-ECNI-MS German Federal Environmental Agency, Laboratory of Water Analysis (Section II 3.5) Experimental Conditions: Matrix: Sediment,suspended particulate matter (SPM) Compounds:BDE-47, BDE-99, BDE-100, BDE-153, BDE-154, (BDE-183, BDE-209) Limit of determination:0.01 to 0.05 µg/kg (test portion 10 g) Extraction: Soxhlet extraction with toluene or hexane/acetone Clean-up: Multi-layer column chromatography on silica gel Detection: GC-ECNI-MS in the selected ion monitoring mode (m/z=79/81 for all congeners except BDE-209) Quantification: ISTD: BDE-77, BDE-181 not occurring in technical mixtures; 13C12-labelled BDE-209

  9. POLYBROMINATED DIPHENYLETHERS (PBDEs) Standardisation German Federal Environmental Agency, Laboratory of Water Analysis (Section II 3.5) FPreaparation of a first working draft by Germany, presentation at the next meeting of ISO/TC 147 „Water Quality“ in Orlando, Florida, May 2002 FNo final desicion with regard to the preferred detection technique and other technical details has been made so far FApproval as committee draft can be expected in 2003 at the earliest

  10. POLYBROMINATED DIPHENYLETHERS (PBDE) Interlaboratory studies German Federal Environmental Agency, Laboratory of Water Analysis (Section II 3.5) First interlaboratory study on PBDEs in 2000 J. de Boer and W. P. Cofino Chemosphere 46 (2002), 625-633 Results for the two sediment samples: Congener RSD in % Assessment BDE-47: 22/24 acceptable BDE-99: 36/45 further improvement necessary BDE-100: 20/20 acceptable BDE-153: 32/37 further improvement necessary BDE-154: 35/45 further improvement necessary BDE-209: 48/78 not under control Second interlaboratory study on PBDEs in 2002 organised by QUASIMEME is under way

  11. POLYCHLOROALKANES C10 to C13 – Challenges 1 German Federal Environmental Agency, Laboratory of Water Analysis (Section II 3.5) FComplex mixture of many thousands of positional isomers 6304 positional isomers assuming no more than one bound chlorine atom on any carbon atom FIncomplete chromatographic separation gas chromatograms of short-chain PCAs show broad humps covering 10 to 15 minutes FLack of specificity when using GC-ECNI-MS at standard ion source operating conditions Monitoring of less charcteristic m/z = 70-73 ions (Cl2-; HCl2-)

  12. POLYCHLOROALKANES C10 to C13 – Challenges 2 German Federal Environmental Agency, Laboratory of Water Analysis (Section II 3.5) FLack of specificity when using GC-ECNI-MS detection at nominal mass potential interferences from PCBs, toxaphenes, and chlordane related compounds FLack of appropriate calibration standards Depending on the degree of chlorination of the calibration standard results can differ from by a factor of ten

  13. POLYCHOROALKANES C10 to C13 – Methods German Federal Environmental Agency, Laboratory of Water Analysis (Section II 3.5) FDehydrochlorination of the PCAs and subsequent determination of the resulting aliphatic hydrocarbons FGas chromatography with electron impact ionisation mass spectrometric detection (GC-MS) POLYCHOROALKANES C10 to C13 – Challenges 1 FGas chromatography with electron capture negative ionisation mass spectrometric detection at high resolution (GC-ECNI-HRMS) FGas chromatography with electron capture negative ionisation mass spectrometric detection at low resolution (GC-ECNI-MS)

  14. POLYCHLOROALKANES C10 to C13 Interlaboratory study German Federal Environmental Agency, Laboratory of Water Analysis (Section II 3.5) First interlaboratory study on PCAs in 1998 G. T. Tomy et al. Analytical Chemistry 71 (1999), 446-451 Results: F Seven laboratories F Two PCA solutions, two fish extracts, PCA-60 commercial formulation of stated concentration F In case of the two PCA solutions deviations fromofup to 74 and 310 %, respectively, were observed F Fish sample1 (only three results) RSD = 27% F Fish sample 2 RSD = 47% Conclusion: F Analysis of PCAs is not under control

  15. POLYCHLOROALKANES C10 to C13 – Standardisation German Federal Environmental Agency, Laboratory of Water Analysis (Section II 3.5) F Analysis of short-chain PCAs is just on the research level at the moment F No standardised procedure will be available in the near future

  16. CONCLUSION 1 German Federal Environmental Agency, Laboratory of Water Analysis (Section II 3.5) FInformation on the required sensitivityof the analytical procedures to develop and on the sample (matrix) type which the Commission has in view to commit for routine monitoring are urgently needed FClose co-operation with groups working on quality standards and monitoring is indispensable FA standardised method for the determination of alkylphenols in surface water samples will soon be available as ISO/DIS

  17. CONCLUSION 2 German Federal Environmental Agency, Laboratory of Water Analysis (Section II 3.5) FThe development of a method for the determination of individual BDE congerers representative of technical Penta-BDE in sediments and SPM is in progress FAnalysis of short-chain PCAs in sediments and SPM is just on the research level FIt can not be foreseen whether a procedure suitable for routine monitoring of PCAs can be developed within reasonable time

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