Recent Advances in High Resolution Mass Spectrometry in Environmental and Petrochemical Analyses

Transcription

1 Recent Advances in High Resolution Mass Spectrometry in Environmental and Petrochemical Analyses Future Fuels Institute, Florida State University National High Magnetic Field Laboratory

2 Petroleomics by FT-ICR To comment on the advantage of one technique is more or less to comment on the disadvantage of the other

3 Peak Capacity = (m/z) max - (m/z) min m 50% m 50% (m/z) min m/z (m/z) max

4 Resolution Requirements for Comprehensive Petroleomics Mass Resolution 1,800K 1,400K 1,000K 600K 1000 m/z 1.1 mda, SH 3 13 C 1 vs. C mda, S 2 H 7 13 C 1 vs. C mda, C 3 vs. SH mda, 13 C 1 vs. CH 200K m/z

5 High-Boiling Polar Molecules Not Resolvable by Chromatography m 2 N S C 23 H C 30 H 53 NS Doublet m 2 -m 1 m 2 -m 1 SH 4 /C mda 135,000 N N C 20 H CC 17 H C 33 H 49 N CC 31 H 46 N 2 C 2 H 3 / 13 CN 17.0 mda 27,000 O/CH mda 13,000 N H 12 /C 93.9 mda 5,000 N O C 13 H C 32 H 45 NO Kuangnan Qian ExxonMobil Research & Engineering N S C 16 H C 31 H 41 NS

6 (Dalton) 0.02 Atomic H 2 H 13 C 14N 15N Mass Defects C 16 O P 32 S 34S

7 This is the way nature works! Low Resolution MS High Resolution MS m m = 2500 m m = 350, m/z

8 How accurate do you have to measure the mass? 10 C c H h N n S s O o Mass Space (1 mda Bins) Mass S. Kim, et al. IJMS 251 (2006)

9 C c H h N n S s O o Mass Space 10 (1 mda Bins) Mass S. Kim, et al. IJMS 251 (2006)

10 C c H h N n S s O o Mass Space 7 (0.5 mda Bins) Mass S. Kim, et al. IJMS 251 (2006)

11 ~1 possibility per bin! C c H h N n S s O o Mass Space 4 (0.1 mda Bins) Mass S. Kim, et al. IJMS 251 (2006)

12 The Current Understanding of Petroleum Composition 1) Distillables 2) Non-distillables 3) Maltenic / Asphaltenic Materials 4) N, S and O Chemistry 5) Current State of Chromatographic Separations 6) Advances in ionization and how it changes current analytical methodology.

13 Single Drop of Oil is ~ 30 mg Dilute to 0.1 mg / ml 300 ml of Stock Solution + ESI - ESI APCI or LIAD APPI 25 L 25 L 25 L 2000 L Total sample consumption is 0.7% of original drop

14 Enabling non-icr Petroleomics by Targeted Analysis Positive Ions N N N O S NS-Compounds NO- Compounds Basic Nitrogen Sulfoxides Negative Ions NH Neutral Nitrogen Naphthenic Acids COOH Sulfur-containing Acids

15 Workflow for High Resolution Petroleomics m/ m 50% m/z * m/z 1. Carbon Number 2. Heteroatom Composition 3. Aromaticity DBE = C H N McLafferty & Turecek Int. Mass Spectra, 1993 [Z = -2(DBE) + n +2] [C 50 H 72 S 1 ] ppb DBE 40 S 1 Class Carbon Number Relative Abundance (% total)

16 POLAR SPECIATION C / H C 2 / C 2 H mda 8.9 mda European Crude Oil (+) ESI FT-ICR MS N 13 C / C 2 H mda O / CH mda C 3 / SH mda N / 13 CH 8.2 mda Formic Acid Modified Solvent System ~8000 peaks > 6σ m/ m50% = 600,000 at 500 m/z m/z ,000

17 African Crude Negative ESI FT-ICR MS Broadband Mass Spectrum No Derivatization Required For Naphthenic Acid Characterization Ammonium Hydroxide Modified Solvent System m/z 1,000 1,200 1,400

18 -ESI 9.4T FT-ICR MS Relative Abundance (% total) O2 Class Image DBE Carbon Number 80 5-Ring 4-Ring 3-Ring 2-Ring 1-Ring Fatty Acids

19 APPI vs. ESI APPI APPI and (+)ESI (-)ESI N S COO H N O NH S

20 But for Sulfur Speciation need very high resolution 49,797 peaks >6 ( m/z) m/ m 50% = 400,000 at m/z scans in 35 minutes Time (s) 14.5T FT-ICR MS m/z

21 +APPI 14.5T FT-ICR MS Relative Abundance (% total) 30 S1 Class Image DBE Carbon Number 70 80

22 The High Resolution Analysis of Saturates Sample Spot on Ti Foil To MS 532 nm Laser O 2 O 2 M M O 2 + H 3 O + N 2 + e - e - OH ~ 2 mm Highest Purity O 2 or N 2 2 mm -2 mm 25 MΩ V

23 Straight-Chain Alkanes C 21 -C 40 [C n H 2n+2 H] [C + 21 H 43 H] + C 21 -C 40 [C 40 H 81 H] L/min O 2 [C n H 2n+2 ] + [C 40 H 82 ] + [C 21 H 44 ] + C 21 -C L/min N m/z

24 (+) AP/LIAD-CI 9.4 T FT-ICR MS of Base Oil 1,754 Peaks > 6σ (159 < m/z < 700) RMS Error = 175 ppb m/ m 50% = m/z 450 * * * * * * 15 Summed Transients * * *[C n H 2n+2 H] + (n = 12 49) * * * * * * * * * * * * * * * * * * * * * * HC [M-H] + m/z * 500 * * * * [C 27 H 48 ] ppm 4.5 mda [C CH 48 -H] ppb m/z 600 H H H H Cholestane (C 27 H 48 ) H DBE 5 % Relative Abundance Carbon Number 50 ( ) n

25 (+) AP/LIAD-CI 9.4 T FT-ICR MS of Deep Water Horizon Crude 4542 peaks > 6σ (140 < m/z < 760) RMS Error 210 ppb m/ m 50% = 700,000 at m/z Summed Transients 30 HC Class ( )n C n H 2n+2 Relative abundance (%) DBE Carbon Number ( ) n ( ) n ( ) n % Relative Abundance 0 HC S 1 N 1 O 1 O 1 S 1 N 1 S 1 O 2 N 2 O 2 Hetero atom class m/z

26 Moving Beyond Thousands of Peaks 106,000 peaks > 6σ 500 < m/z < m/z

27 Where is the useful information? m/ m 50% = 1,300, mda 0 5 Time (s) Quadrupole Isolation (10 Da window) Average 250 peaks across 450 mda m/z

28 Athabasca Bitumen HVGO Distillation Series Positive Ion APPI LTQ-MS IBP-343 C C C C C C C C m/z

29 The Inherent Limitation of Isomerically Resolved Analyses Feed Isomeric Dilution Polarity separation S S S Boiling point separation

30 Toward the Completion of the Petroleome

31 Athabasca Bitumen HVGO Distillation Series Positive-Ion APPI 14.5 T FT-ICR MS Hydrocarbon Class 20 IBP-343 C C C C 16 C 20 DBE = 7 C 26 DBE = 8 C 27 DBE = 8 C 29 DBE = DBE C C C C C 30 DBE = 8 C 33 DBE = 9 C 35 DBE = 9 C 40 DBE= Carbon Number

32 Athabasca Bitumen HVGO Distillation Series Positive-Ion APPI 14.5 T FT-ICR MS S 1 Class 20 IBP-343 C C C C 16 C 18 DBE = 5 C 24 DBE = 6 C 24 DBE = 7 C 26 DBE = DBE C C C C 16 C 28 DBE = 7 C 31 DBE = 8 C 33 DBE = 8 C 39 DBE= Carbon Number

33 Athabasca Bitumen HVGO Distillation Series Positive-Ion APPI 14.5 T FT-ICR MS S 2 Class 20 IBP-343 C C C C C 17 DBE = 6 C 22 DBE = 6.5 C 22 DBE = 7 C 24 DBE = DBE C C C C C 26 DBE = 8 C 28 DBE = 9 C 30 DBE = 9 C 38 DBE= Carbon Number

34 The S 1 Distillable Continuum 60 Combination of 8 individual fractions distilled between 191 C C with the C residue yields a continuum in boiling point, carbon number and aromaticity 40 DBE Relative Abundance (% total) Increasing Boiling Point Carbon Number

35 Distillable Compositional Bounds 60 Defining Maltene Compositional Space 40 DBE Relative Abundance (% total) Increasing Boiling Point Carbon Number

36 The Continuum Model Doesn t Support High MW Asphaltenes 60 Extrapolation to High Molecular Weight C 70,000 = 1.1 DBE Extension to high C# can t account for Asphaltenes Relative Abundance (% total) Increasing Boiling Point Carbon Number

37 The Upper Boundary of the Petroleum Continuum: The Compositional Continuum is now known DBE Relative Abundance (% total) Increasing Boiling Point Carbon Number

38 GC Amenable % Recovered High Resolution MS Temperature ( C)

39 How does an advanced understanding of petroleum composition and advances in ionization enable Petroleomics at lower resolution TARGETED ANALYSIS!!

40 Petroleum Oil Sample sum 50 scans Total analysis time = 2 minutes Ion Accumulation event = 90ms External Calibration is ~ 200 ppb 14.5T (+) ESI FT-ICR MS m/ m ave = 300,000 S-Methylation Experiment Note: ~100 fold decrease in ion accumulation time, 2 fold decrease in detection time, 30 fold better external calibration & ~20 fold decrease in total analysis time compared to similar data collected by APPI. ~2500 peaks identified m/z

41 14.5T +ESI FT-ICR MS Relative Abundance (% total) 20 S Class Image 16 DBE Carbon Number 60

42 Lithium salts Li + cation has affinity for electron donors like O and N atoms Bio-Oils (Corn) Asphaltene Problems in Bio Derived Materials

43 30 O 3 O 4 Li (+ESI) DBE 0 30 TMAH (-ESI) Relative Abundance (% total) Carbon Number

44 +ESI: (M+H) + vs. (M+Ag) + Class distribution comparison for select classes in Canadian bitumen 35 % Relative Abundance (M+H)+ 5 0 S 1 S 2 S 3 HC N 1 N 1 S 1 O 1 S 1 O 1 S 2 O 2 S 2 N 1 O 1 S 1 (M+Ag)+

45 A case study into the application of this methodology to the largest oil spill in US history Gerald Herbert, AP

46 Carolyn Cole, LA Times Chandeleur Mississippi Delta Sound, LouisianaMay Port Fourchon Beach, LA May 25, 2010 Dave Martin, AP Gulf Shores, AL June 5, 2010 Barataria Bay, LA June 6, 2010

47 Pensacola Beach, Florida June 23, 2010 Michael Spooneybarger, AP

48

49 Nelson / Reddy aromatic polar (resins / asphaltene) saturated Macondo well (Deepwater Horizon) biomarkers 74% saturated 16% aromatic 10% polar Reddy et al. (2011) PNAS

50 Nelson / Reddy

51 well sample surface sample sand patty rock scraping Nelson / Reddy

52 Polar fraction: Massive and Persistent Nelson / Reddy April 10 May 10 July 10- Jan 11 April 2011 Chandeleur Island July 2011 FL - AL - MS - LA Nov 11 July 11 MS - LA

53 Oxygenated compounds are being formed Nelson / Reddy

54 5 4.5 Oxygen Weight Percent Macondo Wellhead Pensacola Beach

55 Comprehensive 2D GC X GC Deepwater Horizon Crude Nelson / Reddy Polarity Boiling Point

56 GC x GC Analysis of Deepwater Horizon Crude Oil Aromatics Hopanoids Cycloalkanes Nelson / Reddy Alkane series

57 60 cm September 1, 2010 Pensacola Beach, Florida

58 Macondo NH H HH Nelson / Reddy Ts Tm C 30 -Ts (S) (R) (S) 2HH (R) H Pensacola Beach NH HH Ts Tm C 30 -Ts (S) (R) (S) 2HH (R)

59 (+) ESI FT-ICR MS at 9.4 T 0.1 mg/ml, 2.0% Formic Deepwater Horizon Crude Oil Sum 100 Conditional Co-add 13,700 peaks ± 80 6σ Pensacola Beach Contamination June 30, cm Sum 100 Conditional Co-add 32,232 peaks ± 488 6σ m/z

60 Deepwater Horizon Crude 10 Peaks across 250 mda (+) ESI FT-ICR MS at 9.4 T N 1 N 1 N 1 O 1 N 1 S 1 N 1 O 1 O 1 S 1 13 C 1 N 1 O N 1 O 3 O 13 3 C 1 O 13 2 C 1 N 1 O 2 32 Peaks across 250 mda Pensacola Beach Contamination Core 1, June 30, O 1 13 C 1 N 1 O 2 H 1 C 1 13 C 1 O 2 13 C 1 O 1 13 C 1 m/z

61 5.6 second transient 13 Peaks Detected Resolving Power ~700, seconds processed 14 Peaks Detected Resolving Power ~350, seconds processed 16 Peaks Detected Resolving Power ~175, seconds processed 13 Peaks Resolving Power ~100,

62 Gulf of Mexico Oil Spill Contamination 5.6 second transient 42 Peaks Detected Resolving Power ~700, seconds processed 40 Peaks Detected Resolving Power ~350, seconds processed 25 Peaks Detected Resolving Power ~175, seconds processed 8 Peaks Resolving Power ~100,000 WHY??

63 Macondo Wellhead Petroleum [C 39 H 55 N 1 13 C 1 ] [C 40 H 42 N 13 1 C 1 ] C 3 /SH mda [C 43 H 33 ] [C 42 H 46 ] [C 40 H 38 S 1 ] [C 40 H 54 O 1 ] [C 41 H 58 ] [C 39 H 66 O 1 ] C 3 /SH mda [C 33 H 58 SO 4 ] [C 36 H 54 O 4 ] [C 37 H 58 O 3 ] [C 35 H 50 O 5 ] Tar Ball Cocodrie, LA May 2010 [C 35 H 66 O 4 ] [C 37 H 74 O 2 ] [C 36 H 70 O 3 ] [C 33 H 42 O 7 ] [C 37 H 42 O 4 ] [C 34 H 46 O 6 ] [C 38 H 62 O 2 ] m/z

64 40 (+) ESI (-) ESI Relative Abundance Pensacola Beach Contamination June 30, cm Deepwater Horizon Crude Oil O 6 O 5 O 4 O 3 O 2 O 1 O 1 O 2 O 3 O 4 O 5 O 6 Heteroatom Class

65 211 (+) ESI TOF-MS Representative Model Compounds O Ketones! N 158 N 258 O OH NH m/z

66 LECO GCxGC/MS of oil spill contaminant TIC Alkanes dominate in TIC ion chromatogram at m/z 58 Ketones

67 LECO GCxGC/MS (ion chromatogram for m/z 58) 1 st fraction Alkanes give peak at m/z 58 ( 13 C of m/z 57) 2 nd fraction C 6 C 7 C 8 C 9 C 10 C 11 C 12 Ketones C C C14 C15 C16 C C C 22 C 20 C C C 24 C 26 C 25 C 27 3 rd fraction C 6 C 7 C 8 C 9 C 10 C 11 C 12 Ketones C C C14 C15 C16 C C C 22 C 20 C C C 24 C 26 C 25 C 27

68 Winston K. Robbins Brian Ruddy Robert K. Nelson Christopher M. Reddy Amy M. McKenna NHMFL/FSU Research Funded by NSF Award # DMR NSF Award # CHE July 2009

69