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DVGW-Technologiezentrum Wasser (TZW), Karlsruhe Twinning Project PL06/IB/EN/01 Methods for determination of acrylamide, epichlorohydrin and vinyl chloride.

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Presentation on theme: "DVGW-Technologiezentrum Wasser (TZW), Karlsruhe Twinning Project PL06/IB/EN/01 Methods for determination of acrylamide, epichlorohydrin and vinyl chloride."— Presentation transcript:

1 DVGW-Technologiezentrum Wasser (TZW), Karlsruhe Twinning Project PL06/IB/EN/01 Methods for determination of acrylamide, epichlorohydrin and vinyl chloride Dr. Frank Sacher DVGW-Technologiezentrum Wasser (TZW), Karlsruhe

2 Twinning Project PL06/IB/EN/01 Introduction Analysis of acrylamide Analysis of epichlorohydrin Analysis of vinyl chloride Summary Outline

3 DVGW-Technologiezentrum Wasser (TZW), Karlsruhe Twinning Project PL06/IB/EN/01 Council Directive 98/83/EC on the quality of water intended for human consumption ANNEX I, Part B: Chemical parameters Parameter Parametric value UnitNotes Acrylamide0.10µg/lNote 1 Epichlorohydrin0.10µg/lNote 1 Vinyl chloride0.50µg/lNote 1 Note 1: The parametric value refers to the residual monomer concentration in the water as calculated according to specifications of the maximum release from the corresponding polymer in contact with the water

4 DVGW-Technologiezentrum Wasser (TZW), Karlsruhe Twinning Project PL06/IB/EN/01 Council Directive 98/83/EC on the quality of water intended for human consumption ANNEX III, Part 2: Parameters for which performance characteristics are specified ParameterTruenessPrecisionLODConditionsNotes Acrylamide To be controlled by product specifications Epichlorohydrin Vinyl chloride No analytical determination of acrylamide, epichlorohydrin, and vinyl chloride required!!!

5 DVGW-Technologiezentrum Wasser (TZW), Karlsruhe Twinning Project PL06/IB/EN/01 Some water suppliers using polyacrylamides as coagulation aid calculate the maximum concentration of acryl amide Some water suppliers analyse their finished water for acrylamide, epichlorohydrin, and/or vinyl chloride (independent of their treatment process or materials used in their networks) Most water suppliers do nothing… Practical experiences in Germany

6 DVGW-Technologiezentrum Wasser (TZW), Karlsruhe Twinning Project PL06/IB/EN/01 Number of drinking water samples at TZW Audit monitoring~ 1200~ 1300 Acrylamide5365 Epichlorohydrin156196

7 DVGW-Technologiezentrum Wasser (TZW), Karlsruhe Twinning Project PL06/IB/EN/01 Physical-chemical data: Physical-chemical data:Melting point: 84.5 °C Boiling point: 125 °C (25 mm Hg) Vapor pressure:0.007 mm Hg (20 °C) Water solubility:2160 g/L Source: Source:Monomer for production of polyacrylamides (PAA) PAA are used as coagulant aid in drinking water treatment CAS-No.: Molecular mass: g/mol Acrylamide

8 DVGW-Technologiezentrum Wasser (TZW), Karlsruhe Twinning Project PL06/IB/EN/01 Physical-chemical data: Physical-chemical data:Melting point: - 48 °C Boiling point: °C Density: 1.18 g/cm 3 Water solubility:16 g/L Source: Source:Monomer for production of various plastic materials, especially epoxy resins which might be used for coating of storage reservoirs or as pipe materials in networks for distribution of drinking water CAS-No.: Molecular mass: 92.5 g/mol Epichlorohydrin

9 DVGW-Technologiezentrum Wasser (TZW), Karlsruhe Twinning Project PL06/IB/EN/01 Physical-chemical data: Physical-chemical data:Melting point: °C Boiling point: 14 °C Vapor pressure:3456 mbar (20 °C) Density: g/cm 3 Water solubility:1.1 g/L Source: Source:Monomer for production of PVC which might be used as pipe material Degradation product of PCE and TCE under anaerobic conditions CAS-No.: Molecular mass: 62.5 g/mol Vinyl chloride

10 DVGW-Technologiezentrum Wasser (TZW), Karlsruhe Twinning Project PL06/IB/EN/01 Pre-concentration of the analytes is difficult Liquid-liquid extraction requires large solvent volumes Conventional SPE materials are not suited for polar compounds Chromatography of the analytes is difficult Polarity hampers gas chromatographic determination Retention on conventional reversed-phase HPLC columns is small Detection of the compounds is difficult No chromophor for sensitive UV detection No fluorophor for fluorescence detection No significant masses or mass fragments for MS detection Methods used for other micro-pollutants are not suitable Special methods have to be applied Problems during analysis of small polar molecules

11 DVGW-Technologiezentrum Wasser (TZW), Karlsruhe Twinning Project PL06/IB/EN/01 HPLC/DAD analysis after direct injection (M. Weideborg et al., Water Res. 2001, 35, ) LOD 5 µg/L No specific method Ion-exclusion chromatography with MS detection (S. Cavalli et al., J. Chromatogr. A 2004, 1039, ) LOD 0.2 µg/L Specific detection method GC/MS-MS or GC/ECD analysis after derivatisation with penta- fluorophenyl isothiocyanate (H. Perez et al., Analyst 2003, 128, ) LOD 0.03 µg/L Rather specific method Laborious and time-consuming method Analytical methods for analysis of acrylamide (1)

12 DVGW-Technologiezentrum Wasser (TZW), Karlsruhe Twinning Project PL06/IB/EN/01 Solid-phase extraction on carbon material combined with planar chromatography with fluorescence detection after derivatisation with dansulfinic acid (A. Alpmann et al., J. Sep. Sci. 2008, 31, 71-77) LOD 0.03 µg/L Rather specific method Laborious and time-consuming method Solid-phase extraction on carbon material combined with GC/MS (K. Kawata et al., J. Chromatogr. A 2001, 911, 75-83) LOD 0.02 µg/L Suitability of method for environmental waters is doubtful Analytical methods for analysis of acrylamide (2)

13 DVGW-Technologiezentrum Wasser (TZW), Karlsruhe Twinning Project PL06/IB/EN/01 Evaporation of the water, LC-APCI-MS/MS (S. Chu et al., Anal. Chem. 2007, 79, ) LOD 0.02 µg/L Specific detection method Expensive instrumentation needed Direct large volume injection, LC-MS-MS (J.M. Marin et al., J. Mass. Spectrom. 2006, 41, ) LOD depends on interface LOD 10 µg/L for ESI LOD 0.2 µg/L for APCI Specific detection method Expensive instrumentation needed Analytical methods for analysis of acrylamide (3)

14 DVGW-Technologiezentrum Wasser (TZW), Karlsruhe Twinning Project PL06/IB/EN/01 Solid-phase extraction on activated carbon, LC-ESI-MS/MS Sample volume: 200 mL No pH adjustment Addition of internal standard: d3-acrylamide SPE material: 0.5 g activated carbon Elution: 10 mL methanol Evaporation of the solvent Reconstitution of the dry residue in 100 mL methanol LC column: Phenomenex Luna C18 (150 mm x 3 mm, 3 µm) Eluent: Gradient water/methanol % formic acid Injection volume: 50 µL TZW method for analysis of acrylamide

15 DVGW-Technologiezentrum Wasser (TZW), Karlsruhe Twinning Project PL06/IB/EN/01 TIC Acrylamide Mass: Acrylamide-d 3 Mass: 58 Chromatogram of a µg/L calibration solution

16 DVGW-Technologiezentrum Wasser (TZW), Karlsruhe Twinning Project PL06/IB/EN/01 Calibration curve for acrylamide

17 DVGW-Technologiezentrum Wasser (TZW), Karlsruhe Twinning Project PL06/IB/EN/01 Acrylamide Recovery in %85 Sensitivity in counts/ng0.004 Relative standard deviation in %1.0 Correlation coefficient (r²)0.999 Limit of detection in ng/L1.3 Limit of quantification in ng/L4.7 Validation parameters

18 DVGW-Technologiezentrum Wasser (TZW), Karlsruhe Twinning Project PL06/IB/EN/01 TIC Acrylamide Mass: Acrylamide-d 3 Mass: 58 Detection of acrylamide in drinking water 0.44 µg/L

19 DVGW-Technologiezentrum Wasser (TZW), Karlsruhe Twinning Project PL06/IB/EN/01 Head-space extraction with GC/ECD (L. Lucentini et al., Microchemical J. 2005, 80, 89-98; J. Gaca et al., Analytica Chimica Acta 2005, 540, 55-60) LOD 40 µg/L No specific detection method Purge&trap extraction with GC/ECD (L. Lucentini et al., Microchemical J. 2005, 80, 89-98; J. Gaca et al., Analytica Chimica Acta 2005, 540, 55-60) LOD 0.01 µg/L No specific detection method Solid-phase micro-extraction (SPME) with GC/FID (F.J. Santos et al., J. Chromatogr. A 1996, 742, ) LOD 0.3 µg/L (depending on fiber coating) No specific detection method Analytical methods for analysis of epichlorohydrin (1)

20 DVGW-Technologiezentrum Wasser (TZW), Karlsruhe Twinning Project PL06/IB/EN/01 Principle of Solid-phase micro-extraction (SPME)

21 DVGW-Technologiezentrum Wasser (TZW), Karlsruhe Twinning Project PL06/IB/EN/01 Aqueous-phase aminolysis (derivatisation with 3,5-difluoro- benzylamine), SPE, GC/MS (S.J. Khan et al., Anal. Chem. 2006, 78, ) LOD 0.01 µg/L No specific method, very susceptible to interferences Aqueous-phase derivatisation with sulfite, ion chromatography with conductivity detection or MS detection (M.C. Bruzzoniti et al., J. Chromatogr. A 2000, 884, 251–254; M.C. Bruzzoniti et al., J. Chromatogr. A 2004, 1034, 243–247) LOD 0.1 µg/L (CD) LOD 0.05 µg/L (MSD) CD is no specific detection method; reliability of the derivatisation procedure is doubtful Analytical methods for analysis of epichlorohydrin (2)

22 DVGW-Technologiezentrum Wasser (TZW), Karlsruhe Twinning Project PL06/IB/EN/01 Solid-phase extraction on a styrene-divinyl benzene co-polymer, GC/ECD (H.-J. Neu et al., Fresenius J. Anal. Chem. 1997, 359, 285–287) LOD 0.1 µg/L No specific method Analytical methods for analysis of epichlorohydrin (3) 1 = epichlorohydrin, 2 = 2-chloropropionic acid ethyl ester (internal standard)

23 DVGW-Technologiezentrum Wasser (TZW), Karlsruhe Twinning Project PL06/IB/EN/01 According to EN Solid-phase extraction on SDB material, GC/MS Sample volume: 100 mL No pH adjustment SPE material: 0.2 g SDB material (JT Baker) Elution: 1 mL diisopropylether Addition of internal standard: 2-chloropropionic acid ethyl ester GC column: RTX (30 m x 0.25 mm x 1.40 µm) Injection volume: 2 µL splitless MS detection in SIM mode (m/z = 49, 57, 51, 62) TZW method for analysis of epichlorohydrin

24 DVGW-Technologiezentrum Wasser (TZW), Karlsruhe Twinning Project PL06/IB/EN/01 Calibration curve for epichlorohydrin

25 DVGW-Technologiezentrum Wasser (TZW), Karlsruhe Twinning Project PL06/IB/EN/01 Epichlorohydrin Recovery in %41 Sensitivity in counts/ng0.134 Relative standard deviation in %5.4 Correlation coefficient (r²)0.996 Limit of detection in ng/L35 Limit of quantification in ng/L100 Validation parameters

26 DVGW-Technologiezentrum Wasser (TZW), Karlsruhe Twinning Project PL06/IB/EN/01 Chromatogram of a drinking water sample

27 DVGW-Technologiezentrum Wasser (TZW), Karlsruhe Twinning Project PL06/IB/EN/01 Stability of epichlorohydrin in water

28 DVGW-Technologiezentrum Wasser (TZW), Karlsruhe Twinning Project PL06/IB/EN/01 Stability of epichlorohydrin in diisopropylether

29 DVGW-Technologiezentrum Wasser (TZW), Karlsruhe Twinning Project PL06/IB/EN/01 Head-space extraction with GC/MS (T. Hino et al., J. Chromatogr. A 1998, 810, ) LOD 0.04 µg/L Reliable method Purge&trap extraction with GC/MS (K.-J. Lee et al., Bull. Korean Chem. Soc. 2001, 22, ; E. Martinez et al., J. Chromatogr. A, 2002, 959, ) LOD 0.01 µg/L No specific detection method Analytical methods for analysis of vinyl chloride (1)

30 DVGW-Technologiezentrum Wasser (TZW), Karlsruhe Twinning Project PL06/IB/EN/01 Solid-phase micro-extraction (SPME) with GC/MS (A. Dias Guimaraes et al., Intern. J. Environ. Anal. Chem. 2008, 88, ) LOD 0.25 µg/L (depending on fiber coating) Reliable method Head-space SPME with GC/FID (P. Tölgyessy et al., Petroleum & Coal 2004, 46, 88-94) LOD 0.01 µg/L Method is susceptible to interferences Head-space SPME with GC/MS (M.A. Jochmann et al., Anal. Bioanal. Chem. 2007, 387, 2163–2174) LOD 0.9 µg/L Reliable method Analytical methods for analysis of vinyl chloride (2)

31 DVGW-Technologiezentrum Wasser (TZW), Karlsruhe Twinning Project PL06/IB/EN/01 Purge & Trap GC-MS (similar to EPA method 524.2) Purge & trap system: PTA-3000 from IMT Sorbent material: Tenax Sample volume: 10 mL No pH adjustment Addition of internal standard: bromotrichloromethan Sample temperature: 35 °C Trap temperature: -65 °C Purge time: 15 min GC column: RTX 624 (30 m x 0.32 mm x 1.80 µm) MS detection in SIM mode (m/z = 62, 64) TZW method for analysis of vinyl chloride

32 DVGW-Technologiezentrum Wasser (TZW), Karlsruhe Twinning Project PL06/IB/EN/01 Calibration curve for vinyl chloride

33 DVGW-Technologiezentrum Wasser (TZW), Karlsruhe Twinning Project PL06/IB/EN/01 Vinyl chloride Sensitivity in counts/ng 9.74 Relative standard deviation in %2.4 Correlation coefficient (r²)0.999 Limit of detection in ng/L12 Limit of quantification in ng/L42 Validation parameters

34 DVGW-Technologiezentrum Wasser (TZW), Karlsruhe Twinning Project PL06/IB/EN/01 Chromatogram of a drinking water sample

35 DVGW-Technologiezentrum Wasser (TZW), Karlsruhe Twinning Project PL06/IB/EN/01 Stability of vinyl chloride in water

36 DVGW-Technologiezentrum Wasser (TZW), Karlsruhe Twinning Project PL06/IB/EN/01 European Drinking Water Directive does not require any analytical determination of acrylamide, epichlorohydrin and vinyl chloride but refers to a calculation method Due to their low molecular weight and their high polarity, trace- level analysis of acrylamide, epichlorohydrin and vinyl chloride in drinking waters is a challenging task Recommended method for acrylamide is SPE on carbon material combined with LC/MS-MS detection Recommended method for epichlorohydrin is EN (SPE on SDB material combined with GC/MS) Recommended method for vinyl chloride is purge&trap GC-MS Summary


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