Mark Strynar, Rebecca McMahen, Shuang Liang, Sonia Dagnino, Andrew Lindstrom, Erik Andersen, Larry McMillan, Michael Thurman, Imma Ferrer, Carol Ball

Transcription

1 Determination of perfluoroalkyl ether carboxylic acids (PECAs) and sulfonic acids (PESAs) in North Carolina surface water using high resolution mass spectrometry Mark Strynar, Rebecca McMahen, Shuang Liang, Sonia Dagnino, Andrew Lindstrom, Erik Andersen, Larry McMillan, Michael Thurman, Imma errer, Carol Ball NC AWWA-WEA Conference Wilmington, North Carolina April 13, 2015 ffice of Research and Development April 27, 2015

2 Presentation utline Background on T MS Water sampling effort; routine analysis UPLC-MS/MS; discovery TMS (SETAC 2012 Long Beach CA) Tools used for identification of novel polyfluorinated compound in surface water Sequential water sampling locations Non-targeted screening Negative mass defect Kendrick mass transformation plots ffice of Research and Development 4/27/2015

3 Ex. Mass Accuracy (Tune) = / ^6 = 6.3 ppm Ex Resolution (Tune) / = 24, 720 WHM = ull Width at Half-Height Maximum Resolution in mass spectrometry is the ability to differentiate a detected ion from any other LCGC North America Vol 22 Number 2 ebruary 2004 MS The Practical Art Michael Balough Debating Resolution and Mass Accuracy ffice of Research and Development 4/27/2015

4 Accurate or Monoisotopic Mass The monoisotopic mass is the sum of the masses of the atoms in a molecule using the unbound, ground-state, rest mass of the principal (most abundant) isotope for each element instead of the isotopic average mass. Ex. Carbon 12 C, 13 C, 14 C Hydrogen 1 H, 2 H, 3 H xygen 16, 18 Nitrogen 14 N, 15 N Sulfur 32 S (95.02%) (25 isotopes; 4 stable) luorine 19 ffice of Research and Development 4/27/2015

5 Mass Defect H Accurate Mass Nominal Mass = Mass Defect Ex. PA Nominal Mass: 414 Da Accurate Mass: Da = J Mass Spectrom eb;47(2): doi: /jms The use of mass defect in modern mass spectrometry. Sleno L. ffice of Research and Development

6 Negative Mass Defect: Per- and Poly- fluorinated Compounds ormula Mass C H N P S Cl C 8 H C 8 H C 8 H C 8 H C 8 H 3 S ctane ctanoic acid PA Perfluoro-4-ether-octanoic acid PS Mass fragments of per and poly fluorinated compounds conserve negative mass defect ffice of Research and Development

7 Presentation utline Background on T MS Water sampling effort; routine analysis UPLC-MS/MS; discovery TMS (SETAC 2012 Long Beach CA) Tools used for identification of novel polyfluorinated compound in surface water Sequential water sampling locations Non-targeted screening Negative mass defect Kendrick mass transformation plots ffice of Research and Development 4/27/2015

8 Water Sampling Cape ear River, NC Nakayama et al ES&T 41: ffice of Research and Development 4/27/2015

9 C 008, 009 C 007 ayetteville, NC (Cape ear River) C 005 RC 006 C 004 C 003 C 002 Stream low C 001 ffice of Research and Development

10 Water samples obtained ebruary 2012 Waters WAX SPE Analysis by: (a) UPLC MS/MS routine monitoring PCs (b)tms discovery ffice of Research and Development 4/27/2015

11 Traditional PCs found in Cape ear Water Stream low Analyte C C * PBS C C PHS C C PS C items in red exceed the standard curve high end of 500 ng/l; 10x diluted and re analyzed; * still exceed curve and are estimated ffice of Research and Development

12 Presentation utline Background on T MS Water sampling effort; routine analysis UPLC-MS/MS; discovery TMS Tools used for identification of novel polyfluorinated compound in surface water (update of SETAC 2012 Long Beach CA) Sequential water sampling locations Non-targeted screening Negative mass defect Kendrick mass transformation plots ffice of Research and Development 4/27/2015

13 Workflow for TMS Discovery ffice of Research and Development

14 Control sample; CR 004 Upstream Experiment; CR 002 Downstream Mass Profiler - Agilent 100 largest peaks; each sample Size of circle proportional to peak area; typical usage dosed vs. non-dosed animals ffice of Research and Development

15 Experiment; C 002 Downstream What are all of these compounds? PBA PPeA PHpA Most Have Negative Mass Defect; some appear at same RT ffice of Research and Development

16 Mass Defect Plot TMS data n=483 peaks; both sample + mass defect - mass defect ffice of Research and Development

17 Identified polyfluorinated compound (U2M3HxA) - Target Compound CAS # Molecular ormula = C ormula Weight = Composition = C(21.90%) (63.51%) (14.59%) Monoisotopic Mass = Da [M-H]- = Da Synquest Laboratories - Undecafluoro-2-methyl-3-oxahexanoic acid -3(C 2 ) = (C 2 ) = (C 2 ) = (C 2 ) = (C - 2 ) -2(C 2 ) - (Strynar et al., SETAC 2014 Vancouver, BC Canada) +(C 2 ) ffice of Research and Development -

18 Industry Movement towards shorter chain poly- fluorinated replacement compounds dosed rats ADNA Replacement for AP Reduced toxicity, biological accumulation, persistence? ffice of Research and Development Wang et al., 2013 Environment International 60 (2013)

19 m/z Extracted Ion Chromatograph (EIC) Suspected polyfluorinated compound homologous series -150 amu -3(C 2 ) -100 amu -2(C 2 ) -50 amu -(C 2 ) amu +(C 2 ) +100 amu +2(C 2 ) ffice of Research and Development

20 m/z Extracted Ion Chromatograph (EIC) 329 * 2 = ffice of Research and Development Standard or extracted water, same spectra. m/z 328 LW

21 Key TMS Information Difference Between Peaks Na + ( ) -H + (1.0073) = [M-H] - [M-H] - H + [M-H] - [M-H] - Na ffice of Research and Development

22 Isotope Cluster Scoring Ex. C 12 H % 1. Accurate mass [M] 2. Isotope Abundance [%] 13% 3. Isotope Spacing [m/z] 4% 0.5% ffice of Research and Development

23 2[M-H]- Na+ ragment 1 [M-H]- [M] ragment 2 [M] ffice of Research and Development

24 Homologous series: [M-H] -, [M 2 -H] -, [M-H] - 2Na +, All have m/z offset peaks -3(C 2 ) -2(C 2 ) -(C 2 ) ffice of Research and Development

25 ffice of Research and Development H Na + C - C - (B) [M-H] - = C m/z = H + Additional Polyfluorinated Compounds Continued to see m/z offset peaks +/- C 2 showed no peaks [M-1]/2 754/2~377 [M-22]/ /2~377

26 2[M-H]- Na+ ragment 1 [M-H]- [M] 2[M-H]- Na+ H 2 [M] No spectra available ffice of Research and Development

27 Homologous series NT offset C 2 BUT C 2 H Molecular ormula = C 6 H 11 6 Monoisotopic Mass = Da [M-H]- = Da H Molecular ormula = C 5 H 9 5 Monoisotopic Mass = Da [M-H]- = Da H Molecular ormula = C 4 H 7 4 Monoisotopic Mass = Da [M-H]- = Da H Molecular ormula = C 3 H 5 3 Monoisotopic Mass = Da [M-H]- = Da ffice of Research and Development

28 Additional n-mers* Proton Bound Dimer Sodium Bound Dimer [M-H] - Sodium Bound Trimer Sodium Bound Tetramer * Trier, X.; Granby, K.; Christensen, J. H., Tools to discover anionic and nonionic polyfluorinated alkyl surfactants by liquid chromatography electrospray ionisation mass spectrometry. J. Chromatogr. A 2011, 1218, (40), ffice of Research and Development

29 Portal/ ffice of Research and Development

30 Nafion html?rid=adf15395-d088-4a3b-9df8-3298ea7c800b Nafion is a sulfonated tetrafluoroethylene based fluoropolymer-copolymer. H proton conductor for proton exchange S membrane (PEM) fuel cells Molecular ormula = C 7 H 13 5 S Monoisotopic Mass = Da [M-H]- = Da ffice of Research and Development

31 H S Nafion Molecular ormula = C 7 H 13 5 S Monoisotopic H Mass CA = Da [M-H]- = Da Nafion +H CR004 & upstream H H H S Nafion Molecular ormula: C 7 H S CATP Monoisotopic H Mass: Da [M-H]-: Da +H CR003 Nafion & downstream TP Molecular ormula: C 8 H 13 4 Monoisotopic Mass: Da [M-H]-: Da Molecular ormula: C 8 H Monoisotopic Mass: Da [M-H]-: Da ffice of Research and Development

32 Kendrick Mass Defect Transformations Kendrick Mass () = (observed mass) X Nominal mass Exact mass If () = C 2 Nominal mass Exact mass = Kendrick, Edward (1963) Anal. Chem. 35 (13) ffice of Research and Development

33 Kendrick Mass Defect Standards Example Kendrick Kendrick RT mass [M-H]- Nominal Mass C2 mass mass defect PS sulfonates PDS PHpS PBS phosphinic phosphinic acids phosphinic phosphinic phosphinic phosphinic C4 carboxylic acids C C C C C C :2 ts telomer sulfonates :2 ts C4 -C2 decarboxylated acids C5 -C C7 - C C9 -C C8 -C C10 -C C6 - C2 ffice of Research and Development

34 C 2 = 50/ C 2 = 66/ ffice of Research and Development Kendrick Mass Defect Water Example Kendrick Kendrick Kendrick Kendrick RT(Cape mass ear abundance River [M-H]- Water) Truncate C2 mass C2 mass C2 mass defect C2 mass defect upstream downstream

35 Aknowledgements U.S. EPA RTP Team Andy Lindstrom, Rebecca McMahen, Mark Strynar, Shuang Liang, Erik Andersen (Navy-Japan), Sonia Dagnino (U. of AZ-Tuscon), Larry McMillan Co-authors Mike Thurman, Imma errer, Carol Ball) Joe Weitzel ollow-up Sampling: Detlef Knappe, Elisa Arevalo ffice of Research and Development Questions?