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

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.

EPA Method 537

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.

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

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

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

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.

Thermo PFOA Analysis Kit

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

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.

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

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

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

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

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

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

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

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

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

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

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

Unregulated Contaminant Monitoring Rules 3 (UCMR3)

UCMR 3 Contaminants and Corresponding Analytical Methods - PFCs

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

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

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