dvgw-technologiezentrum wasser (tzw), karlsruhe twinning project pl06/ib/en/01 methods for...

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




Introduction

Analysis of acrylamide

Analysis of epichlorohydrin

Analysis of vinyl chloride

Summary

OutlineOutline



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

ParameterParametric

valueUnit 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



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!!!



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



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



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

H2C CH CO

NH2

CAS-No.: 79-06-1

Molecular mass: 71.08 g/mol

AcrylamideAcrylamide



Physical-chemical data:Physical-chemical data: Melting point: - 48 °C

Boiling point: 116.5 °C

Density: 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


EpichlorohydrinEpichlorohydrin

H2C CHO

CH2Cl



Physical-chemical data:Physical-chemical data: Melting point: - 159 °C

Boiling point: 14 °C

Vapor 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


Vinyl chlorideVinyl chloride

C CH

H

H

Cl



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 moleculesProblems during analysis of small polar molecules



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)



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




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




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



RT: 0.00 - 8.00 SM: 7B

0 1 2 3 4 5 6 7 8Time (min)

0

200000

400000

600000

800000

1000000

1200000

1400000

1600000

0

50000

100000

150000

200000

250000

300000

350000

Inte

nsi

ty

0

200000

400000

600000

800000

1000000

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



0 20 40 60 80 1000.00

0.05

0.10

0.15

0.20

0.25

0.30

0.35

0.40

are

a r

ati

o

amount / ng/L

Calibration curve for acrylamideCalibration curve for acrylamide



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



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)

0

500000

1000000

1500000

2000000

2500000

3000000

3500000

4000000

0

1000000

2000000

3000000

4000000

5000000

Inte

nsi

ty

0

1000000

2000000

3000000

4000000

5000000

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



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)



Principle of Solid-phase micro-extraction (SPME)Principle of Solid-phase micro-extraction (SPME)



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




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)



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



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

rat

io

amount / ng/L



Epichlorohydrin

Recovery in % 41




Limit of detection in ng/L 35

Limit of quantification in ng/L 100




Chromatogram of a drinking water sampleChromatogram of a drinking water sample



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

Pea

k ar

ea r

atio

Drinking waterRiver Rhine water

c0 = 3 µg/L



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

Pea

k ar

ea r

atio

c0 = 3 µg/L



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)



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)



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



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

4.0a

rea

ra

tio

amount / ng/L



Vinyl chloride




Limit of detection in ng/L 12

Limit of quantification in ng/L 42




Chromatogram of a drinking water sampleChromatogram of a drinking water sample



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 20

Time in days

Co

nce

ntr

atio

n i

n µ

g/L

Drinking waterRiver Rhine water



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

dvgw-technologiezentrum wasser (tzw), karlsruhe twinning project pl06/ib/en/01 methods for...

Documents

water slide

karlsruhe slide

water suppliers

c water solubility

quality of water

finished water

gmol acrylamide slide

gmol vinyl chloride