methods for determination of acrylamide, epichlorohydrin and vinyl chloride
DESCRIPTION
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. - PowerPoint PPT PresentationTRANSCRIPT
DVGW-Technologiezentrum Wasser (TZW), Karlsruhe
Twinning Project PL06/IB/EN/01
Methods for determination of Methods for determination of acrylamide, epichlorohydrin and acrylamide, epichlorohydrin and
vinyl chloridevinyl chloride
Dr. Frank Sacher
DVGW-Technologiezentrum Wasser (TZW), Karlsruhe
DVGW-Technologiezentrum Wasser (TZW), Karlsruhe
Twinning Project PL06/IB/EN/01
Introduction
Analysis of acrylamide
Analysis of epichlorohydrin
Analysis of vinyl chloride
Summary
OutlineOutline
DVGW-Technologiezentrum Wasser (TZW), Karlsruhe
Twinning Project PL06/IB/EN/01
Council Directive 98/83/EC on the quality of water Council Directive 98/83/EC on the quality of water intended for human consumptionintended for human consumption
ANNEX I, Part B: Chemical parameters
Parameter Parametric value Unit Notes
Acrylamide 0.10 µg/l Note 1
Epichlorohydrin 0.10 µg/l Note 1
Vinyl chloride 0.50 µg/l Note 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
DVGW-Technologiezentrum Wasser (TZW), Karlsruhe
Twinning Project PL06/IB/EN/01
Council Directive 98/83/EC on the quality of water Council Directive 98/83/EC on the quality of water intended for human consumptionintended for human consumption
ANNEX III, Part 2: Parameters for which performance characteristics are specified
Parameter Trueness Precision LOD Conditions Notes
Acrylamide To be controlled by
product specifications
Epichlorohydrin
Vinyl chloride
No analytical determination of acrylamide, epichlorohydrin, and vinyl chloride required!!!
DVGW-Technologiezentrum Wasser (TZW), Karlsruhe
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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 GermanyPractical experiences in Germany
DVGW-Technologiezentrum Wasser (TZW), Karlsruhe
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Number of drinking water samples at TZWNumber of drinking water samples at TZW
2007 2008
Audit monitoring ~ 1200 ~ 1300
Acrylamide 53 65
Epichlorohydrin 156 196
DVGW-Technologiezentrum Wasser (TZW), Karlsruhe
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Physical-chemical data:Physical-chemical data: Melting point: 84.5 °CBoiling 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
H2C CH CO
NH2
CAS-No.: 79-06-1
Molecular mass: 71.08 g/mol
AcrylamideAcrylamide
DVGW-Technologiezentrum Wasser (TZW), Karlsruhe
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Physical-chemical data:Physical-chemical data: Melting point: - 48 °CBoiling point: 116.5 °CDensity: 1.18 g/cm3
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.: 106-89-8
Molecular mass: 92.5 g/mol
EpichlorohydrinEpichlorohydrin
H2C CHO
CH2Cl
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Physical-chemical data:Physical-chemical data: Melting point: - 159 °CBoiling point: 14 °CVapor pressure: 3456 mbar (20 °C)Density: 0.911 g/cm3
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.: 75-01-4
Molecular mass: 62.5 g/mol
Vinyl chlorideVinyl chloride
C CH
H
H
Cl
DVGW-Technologiezentrum Wasser (TZW), Karlsruhe
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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 suitableSpecial methods have to be applied
Problems during analysis of small polar moleculesProblems during analysis of small polar molecules
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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 Analytical methods for analysis of acrylamideacrylamide (1) (1)
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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 Analytical methods for analysis of acrylamideacrylamide (2) (2)
DVGW-Technologiezentrum Wasser (TZW), Karlsruhe
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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
Analytical methods for analysis of Analytical methods for analysis of acrylamideacrylamide (3) (3)
DVGW-Technologiezentrum Wasser (TZW), Karlsruhe
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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
TZW method for analysis of TZW method for analysis of acrylamideacrylamide
DVGW-Technologiezentrum Wasser (TZW), Karlsruhe
Twinning Project PL06/IB/EN/01
RT: 0.00 - 8.00 SM: 7B
0 1 2 3 4 5 6 7 8Time (min)
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Acrylamid TIC
RT: 2.97SN: 106
RT: 2.98SN: 58
RT: 2.66SN: 5
Acrylamid D3
RT: 2.98SN: 137
NL: 1.12E6TIC MS Genesis KP_ang_151008
NL: 3.75E5TIC F: + c ESI sid=12.00 SRM ms2 [email protected] [43.985-44.185, 54.967-55.167] MS Genesis KP_ang_151008
NL: 1.63E6TIC F: + c ESI sid=10.00 SRM ms2 [email protected] [57.982-58.182] MS Genesis KP_ang_151008
TIC
AcrylamideMass: 44 + 55
Acrylamide-d3
Mass: 58
Chromatogram of a 0.075 µg/L calibration solutionChromatogram of a 0.075 µg/L calibration solution
DVGW-Technologiezentrum Wasser (TZW), Karlsruhe
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0 20 40 60 80 1000.00
0.05
0.10
0.15
0.20
0.25
0.30
0.35
0.40
area
ratio
amount / ng/L
Calibration curve for acrylamideCalibration curve for acrylamide
DVGW-Technologiezentrum Wasser (TZW), Karlsruhe
Twinning Project PL06/IB/EN/01
Acrylamide
Recovery in % 85
Sensitivity in counts/ng 0.004
Relative standard deviation in % 1.0
Correlation coefficient (r²) 0.999
Limit of detection in ng/L 1.3
Limit of quantification in ng/L 4.7
Validation parametersValidation parameters
DVGW-Technologiezentrum Wasser (TZW), Karlsruhe
Twinning Project PL06/IB/EN/01
TIC
AcrylamideMass: 44 + 55
Acrylamide-d3
Mass: 58
Detection of acrylamide in drinking waterDetection of acrylamide in drinking waterRT: 0.00 - 8.00 SM: 7B
0 1 2 3 4 5 6 7 8Time (min)
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Acrylamid TIC
RT: 2.98SN: 194
RT: 2.99SN: 138
Acrylamid D3
RT: 2.98SN: 238
NL: 5.23E6TIC MS Genesis Sample_02
NL: 5.67E6TIC F: + c ESI sid=12.00 SRM ms2 [email protected] [43.985-44.185, 54.967-55.167] MS Genesis Sample_02
NL: 4.42E6TIC F: + c ESI sid=10.00 SRM ms2 [email protected] [57.982-58.182] MS Genesis Sample_02
0.44 µg/L
DVGW-Technologiezentrum Wasser (TZW), Karlsruhe
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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 Analytical methods for analysis of epichlorohydrinepichlorohydrin (1) (1)
DVGW-Technologiezentrum Wasser (TZW), Karlsruhe
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Principle of Solid-phase micro-extraction (SPME)Principle of Solid-phase micro-extraction (SPME)
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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 Analytical methods for analysis of epichlorohydrinepichlorohydrin (2) (2)
DVGW-Technologiezentrum Wasser (TZW), Karlsruhe
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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 Analytical methods for analysis of epichlorohydrinepichlorohydrin (3) (3)
1 = epichlorohydrin, 2 = 2-chloropropionic acid ethyl ester (internal standard)
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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)
TZW method for analysis of TZW method for analysis of epichlorohydrinepichlorohydrin
DVGW-Technologiezentrum Wasser (TZW), Karlsruhe
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Calibration curve for epichlorohydrinCalibration curve for epichlorohydrin
0 100 200 300 400 5000.00
0.01
0.02
0.03
0.04
0.05
0.06
area
ratio
amount / ng/L
DVGW-Technologiezentrum Wasser (TZW), Karlsruhe
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Epichlorohydrin
Recovery in % 41
Sensitivity in counts/ng 0.134
Relative standard deviation in % 5.4
Correlation coefficient (r²) 0.996
Limit of detection in ng/L 35
Limit of quantification in ng/L 100
Validation parametersValidation parameters
DVGW-Technologiezentrum Wasser (TZW), Karlsruhe
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Chromatogram of a drinking water sampleChromatogram of a drinking water sample
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Stability of epichlorohydrin in waterStability of epichlorohydrin in water
0.000
0.002
0.004
0.006
0.008
0.010
0.012
0.014
0.016
0.018
0.020
0 5 10 15 20 25 30 35 40 45
Time in days
Peak
are
a ra
tio
Drinking waterRiver Rhine water
c0 = 3 µg/L
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Stability of epichlorohydrin in diisopropyletherStability of epichlorohydrin in diisopropylether
0.00
0.01
0.02
0.03
0.04
0.05
0.06
0.07
0.08
0.09
0.10
0 5 10 15 20 25 30 35 40 45
Time in days
Peak
are
a ra
tio
c0 = 3 µg/L
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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 Analytical methods for analysis of vinyl chloridevinyl chloride (1) (1)
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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
Analytical methods for analysis of Analytical methods for analysis of vinyl chloridevinyl chloride (2) (2)
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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 TZW method for analysis of vinyl chloridevinyl chloride
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Calibration curve for vinyl chlorideCalibration curve for vinyl chloride
0 50 100 150 200 250 300 350 400 4500.0
0.5
1.0
1.5
2.0
2.5
3.0
3.5
4.0ar
ea ra
tio
amount / ng/L
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Vinyl chloride
Sensitivity in counts/ng 9.74
Relative standard deviation in % 2.4
Correlation coefficient (r²) 0.999
Limit of detection in ng/L 12
Limit of quantification in ng/L 42
Validation parametersValidation parameters
DVGW-Technologiezentrum Wasser (TZW), Karlsruhe
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Chromatogram of a drinking water sampleChromatogram of a drinking water sample
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Stability of vinyl chloride in waterStability of vinyl chloride in water
0.0
0.1
0.2
0.3
0.4
0.5
0.6
0 2 4 6 8 10 12 14 16 18 20Time in days
Con
cent
ratio
n in
µg/
L
Drinking waterRiver Rhine water
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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
SummarySummary