Methods for determination of acrylamide epichlorohydrin and vinyl chloride
Download
1 / 36

Methods for determination of acrylamide, epichlorohydrin and vinyl chloride - PowerPoint PPT Presentation


  • 92 Views
  • Uploaded on

Methods for determination of acrylamide, epichlorohydrin and vinyl chloride. Dr. Frank Sacher DVGW-Technologiezentrum Wasser (TZW), Karlsruhe. Outline. Introduction Analysis of acrylamide Analysis of epichlorohydrin Analysis of vinyl chloride Summary.

loader
I am the owner, or an agent authorized to act on behalf of the owner, of the copyrighted work described.
capcha
Download Presentation

PowerPoint Slideshow about ' Methods for determination of acrylamide, epichlorohydrin and vinyl chloride' - ardelle-york


An Image/Link below is provided (as is) to download presentation

Download Policy: Content on the Website is provided to you AS IS for your information and personal use and may not be sold / licensed / shared on other websites without getting consent from its author.While downloading, if for some reason you are not able to download a presentation, the publisher may have deleted the file from their server.


- - - - - - - - - - - - - - - - - - - - - - - - - - E N D - - - - - - - - - - - - - - - - - - - - - - - - - -
Presentation Transcript
Methods for determination of acrylamide epichlorohydrin and vinyl chloride

Methods for determination of acrylamide, epichlorohydrin and vinyl chloride

Dr. Frank Sacher

DVGW-Technologiezentrum Wasser (TZW), Karlsruhe


Outline vinyl chloride

  • Introduction

  • Analysis of acrylamide

  • Analysis of epichlorohydrin

  • Analysis of vinyl chloride

  • Summary


Council Directive 98/83/EC on the quality of water intended for human consumption

  • ANNEX I, Part B: Chemical parameters

  • 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


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

  • No analytical determination of acrylamide, epichlorohydrin, and vinyl chloride required!!!


Practical experiences in Germany for human consumption

  • 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…



Acrylamide for human consumption

CAS-No.: 79-06-1

Molecular mass: 71.08 g/mol

  • 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: Monomer for production of polyacrylamides (PAA) PAA are used as coagulant aid in drinking water treatment


Epichlorohydrin for human consumption

CAS-No.: 106-89-8

Molecular mass: 92.5 g/mol

  • Physical-chemical data: Melting point: - 48 °C Boiling point: 116.5 °C Density: 1.18 g/cm3Water solubility:16 g/L

  • 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


Vinyl chloride for human consumption

CAS-No.: 75-01-4

Molecular mass: 62.5 g/mol

  • Physical-chemical data: Melting point: - 159 °C Boiling point: 14 °C Vapor pressure: 3456 mbar (20 °C) Density: 0.911 g/cm3Water solubility:1.1 g/L

  • Source: Monomer for production of PVC which might be used as pipe material Degradation product of PCE and TCE under anaerobic conditions


Problems during analysis of small polar molecules for human consumption

  • 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


Analytical methods for analysis of for human consumptionacrylamide (1)

  • HPLC/DAD analysis after direct injection (M. Weideborg et al., Water Res. 2001, 35, 2645-2652)

    • LOD ≈ 5 µg/L

    • No specific method

  • Ion-exclusion chromatography with MS detection (S. Cavalli et al., J. Chromatogr. A 2004, 1039, 155-159)

    • 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, 1033-1036)

    • LOD ≈ 0.03 µg/L

    • Rather specific method

    • Laborious and time-consuming method


Analytical methods for analysis of for human consumptionacrylamide (2)

  • 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 for human consumptionacrylamide (3)

  • Evaporation of the water, LC-APCI-MS/MS (S. Chu et al., Anal. Chem. 2007, 79, 5093-5096)

    • 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, 1041-1048)

    • LOD depends on interface

      • LOD ≈ 10 µg/L for ESI

      • LOD ≈ 0.2 µg/L for APCI

    • Specific detection method

    • Expensive instrumentation needed


TZW method for analysis of for human consumptionacrylamide

  • 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 + 0.1 % formic acid

    • Injection volume: 50 µL


Chromatogram of a 0.075 µg/L calibration solution for human consumption

TIC

Acrylamide

Mass: 44 + 55

Acrylamide-d3

Mass: 58


Calibration curve for acrylamide for human consumption


Validation parameters for human consumption


Detection of acrylamide in drinking water for human consumption

TIC

Acrylamide

Mass: 44 + 55

Acrylamide-d3

Mass: 58

  • 0.44 µg/L


Analytical methods for analysis of for human consumptionepichlorohydrin (1)

  • 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, 181-189)

    • LOD ≈ 0.3 µg/L (depending on fiber coating)

    • No specific detection method



Analytical methods for analysis of for human consumptionepichlorohydrin (2)

  • Aqueous-phase aminolysis (derivatisation with 3,5-difluoro-benzylamine), SPE, GC/MS (S.J. Khan et al., Anal. Chem. 2006, 78, 2608-2616)

    • 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 for human consumptionepichlorohydrin (3)

  • 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

1 = epichlorohydrin, 2 = 2-chloropropionic acid ethyl ester (internal standard)


TZW method for analysis of for human consumptionepichlorohydrin

  • According to EN 14207

  • 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 502.2 (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)



Validation parameters for human consumption





Analytical methods for analysis of for human consumptionvinyl chloride (1)

  • Head-space extraction with GC/MS (T. Hino et al., J. Chromatogr. A 1998, 810, 141-147)

    • LOD ≈ 0.04 µg/L

    • Reliable method

  • Purge&trap extraction with GC/MS (K.-J. Lee et al., Bull. Korean Chem. Soc. 2001, 22, 171-178; E. Martinez et al., J. Chromatogr. A, 2002, 959, 181-190)

    • LOD ≈ 0.01 µg/L

    • No specific detection method


Analytical methods for analysis of for human consumptionvinyl chloride (2)

  • Solid-phase micro-extraction (SPME) with GC/MS (A. Dias Guimaraes et al., Intern. J. Environ. Anal. Chem. 2008, 88, 151-164)

    • 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


TZW method for analysis of for human consumptionvinyl chloride

  • 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)



Validation parameters for human consumption




Summary for human consumption

  • 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 14207 (SPE on SDB material combined with GC/MS)

  • Recommended method for vinyl chloride is purge&trap GC-MS


ad