1. Analysis of Perfluorinated Compounds (PFCs) by Liquid Chromatography/Mass Spectrometry
Jia Wang
April 11, 2013

2. Perfluorinated Compounds
Stain, oil and water resistant
Chemical and thermo stability
Applied to fabrics, papers, carpets, and fire-fighting foam
Persistent, bioaccumulative and toxic
PFOA and PFOS now on CCL3 list (Contaminant Candidate List 3)
Perfluorinated compounds (PFCs) are an emerging class of environmental contaminants.

3. EPA Method 537

4. Lancaster Laboratories and Thermo Fisher Scientific Participated in the Second Laboratory Demonstration of EPA Method 537
Good separation and recovery of fourteen perfluorinated alkyl acids in fortified reagent water and drinking water under conditions of EPA method 537.
Sensitivity in ppt range for all analytes listed in EPA Method 537.
The performance of EPA method 537 was demonstrated, with results similar to those reported in the method.

5. Compounds Analyzed * Technical Grade: both linear and branched isomers
Note: Alternative column is evaluated for the possibility of analyzing all three groups of compounds using one column
* Technical Grade: both linear and branched isomers

6. EPA Method 537 LC and ESI-MS Conditions
Mobile phase: 20 mM ammonium acetate and methanol
Injection solvent: 96:4% (vol/vol) methanol:water
Injection volume: 10 L
Flow rate: 0.3 mL/min
Electrospray ionization (ESI): Negative
LC gradient
Time (min)
% 20 mM ammonium acetate
% Methanol 60 40 1 25 10 90 32
32.1 37
Note: Alternative column is evaluated for the possibility of analyzing all three groups of compounds using one column

7. Sample Preparation
Preservation reagent: Trizma® Preset Crystals, pH 7.0, 1.25 g/250 mL
250 mL water fortified with surrogates is extracted by SPE and eluted by methanol
SPE cartridges: styrenedivinylbenzene (SDVB) sorbent, 0.5g/6mL
The extract was concentrated to dryness and then adjusted to a 1 mL volume with 96:4% (vol/vol) methanol: water
Note: Alternative column is evaluated for the possibility of analyzing all three groups of compounds using one column

8. PFCs Analysis Challenge
Method interferences may be caused by contaminants in solvents, reagents, sample bottles and caps, and other sample processing hardware that lead to discrete artifacts and/or elevated baselines in the chromatograms.
The method analytes in this method can also be found in many common laboratory supplies and equipment, such as PTFE (polytetrafluoroethylene) products, LC solvent lines, methanol, aluminum foil, SPE sample transfer lines, etc.
All items such as these must be routinely demonstrated to be free from interferences (less than 1/3 the MRL for each method analyte) under the conditions of the analysis by analyzing laboratory reagent blanks.
Subtracting blank values from sample results is not permitted.
Method interferences may be caused by contaminants in solvents, reagents (including reagent water), sample bottles and caps, and other sample processing hardware that lead to discrete artifacts and/or elevated baselines in the chromatograms.
The method analytes in this method can also be found in many common laboratory supplies and equipment, such as PTFE (polytetrafluoroethylene) products, LC olvent lines, methanol, aluminum foil, SPE sample transfer lines, etc.
All items such as these must be routinely demonstrated to be free from interferences (less than 1/3 the MRL for each method analyte) under the conditions of the analysis by analyzing laboratory reagent blanks.
Subtracting blank values from sample results is not permitted.

9. Thermo PFOA Analysis Kit

10. LC System Modification
PTFE solvent frits and tubing were replaced by PEEK solvent frits and tubing
Degasser was replaced by PFOA free degasser
A trapping column (Thermo BDS-Hypersil, C8, 3 x 150 mm, 5 m) was placed between the pump outlet module and autosampler to trap and separate PFCs contaminant from analytes

11. LC and ESI MS Conditions
Instrument: Thermo Fisher Scientific Dionex XRS Pump, Accela Open Autosampler, and TSQ Quantum Vantage
Analytical Column: Thermo Scientific Accucore C18 column (3 x 150 mm, 2.6 m)
Mobile phase: 20 mM ammonium acetate and methanol
Electrospray ionization (ESI): Negative
Time (min)
% 20 mM ammonium acetate
% Methanol 70 30 1 25 10 90 32
32.1 37
Perfluorinated compounds (PFCs) are an emerging class of environmental contaminants.

12. PFC Contaminants are Separated from Analytes - 0.1 ppb
PFBS
PFHxA
PFHxA-SUR
PFHpA
PFHxS*
PFOA
Note: Alternative column is evaluated for the possibility of analyzing all three groups of compounds using one column
PFOA Contaminant
* Technical grade

13. PFC Contaminants are Separated from Analytes - 0.1 ppb
PFOA-IS
PFNA
PFOS*
PFOS-IS
PFDA
PFDA-SUR
NMeFOSAA-IS
Note: Alternative column is evaluated for the possibility of analyzing all three groups of compounds using one column
* Technical grade

14. PFC Contaminants are Separated from Analytes - 0.1 ppb
NMeFOSAA
PFUnA
NEtFOSAA-SUR
NEtFOSAA
PFDoA
PFTrDA
PFTA
Note: Alternative column is evaluated for the possibility of analyzing all three groups of compounds using one column

15. TraceFinder Software
PFC acquisition and analysis was performed using software with built-in workflows for streamlining method development and routine analysis.

16. Compound Database
Note: Alternative column is evaluated for the possibility of analyzing all three groups of compounds using one column

17. Method Development
Note: Alternative column is evaluated for the possibility of analyzing all three groups of compounds using one column

18. Method Development
Note: Alternative column is evaluated for the possibility of analyzing all three groups of compounds using one column

19. Data Review – PFOA
Note: Alternative column is evaluated for the possibility of analyzing all three groups of compounds using one column

20. Data Review – PFOS
Note: Alternative column is evaluated for the possibility of analyzing all three groups of compounds using one column

21. Data Review – PFOS
Note: Alternative column is evaluated for the possibility of analyzing all three groups of compounds using one column

22. Report View
Note: Alternative column is evaluated for the possibility of analyzing all three groups of compounds using one column

23. Unregulated Contaminant Monitoring Rules 3 (UCMR3)

24. UCMR 3 Contaminants and Corresponding Analytical Methods - PFCs

25. Thermo Has Helped Customer to Receive UCMR3 Certification for EPA Method 537
EPA coordinates a Laboratory Approval Program for the contaminants. UCMR 3 requires laboratories have EPA approval to analyze PWS samples.
Thermo Fisher Scientific has developed TraceFinder method for EPA method 537 UCMR3 analysis. Our customer has used this TraceFinder method for EPA method 537 UCMR3 application and PT samples analysis, and received EPA certification

26. Summary
Thermo Fisher Scientific offers PFOA analysis kit to reduce and separate PFCs contaminants from analytes
Thermo Fisher Scientific and Lancaster Labs had previously participated in the second laboratory demonstration of EPA Method 537
Thermo Fisher Scientific has developed TraceFinder method for EPA method 537 UCMR3 analysis. Customer has used this TraceFinder method for EPA method 537 UCMR3 analysis and received EPA certification
Note: Alternative column is evaluated for the possibility of analyzing all three groups of compounds using one column

27. Thank You for Your Attention
Questions?