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Capillary electrophoresis-mass
spectrometry technology for the
analysis of naphthenic acid fraction
compounds in oil sands...
Contents
• Instrumentation setup
• Sample preparation
• Three “modes of attack” for NAs
• Results workup
2
Flow-through Microvial Interface
for CE-ESI-MS
Maxwell, E. J.; Zhong, X.; Zhang, H.; van Zeijl, N.; Chen, D. D. Y. Electro...
EDC-NHS Derivatization(s) of
naphthenic acids
4
Hermanson, G. T. Bioconjugate Techniques; 2nd ed.; Elsevier Inc., 2008; p....
5
Three modes of attack
Capillary Zone
Electrophoresis
Field Amplified
Sample
Injection
Polarity
Switching
Nonaqueous
capill...
Capillary Zone Electrophoresis (CZE)
• All three derivatization mixtures
• Capillary 50 μm i.d., coated with PEI(+)
• Smal...
EDC derivatization of NAs
8
EDC-NHS derivatization of NAs
9
10
EDC-Sulfo-NHS derivatization of NAs
11
C10
Z=0,-2
C11
Z=0,-2,-4
C12
Z=0,-2,-4
C13
Z=0,-2,-4
C14
Z=0,-2,-4
C15
Z=0,-2,-4
C16
Z=0,-2,-4
12
13
Field-Amplified Sample Injection (FASI)
• Short plug of water introduced into the
capillary (0.5 psi 10 sec)
• Sample inje...
15
Field-Amplified Sample Injection (FASI)
EDC EDC-NHS EDC-Sulfo-NHS
16
A.
B.
C.
D.
E.
E.
17
1.460
1.457
1.461
1.504
1.514
1.524
4
10
14
18
45 amu
A.
B.
C.
D.
E.
E.
19
20
Field Amplified Sample Injection with
Polarity Switching (FASI-PSw)
• Begin with FASI
• Separate with -30 kV
• At ~8.3 min...
22
S
EOF (+ESI)-MS
23
Weak pH/solubility gradient
Britz-McKibbin, P.; Chen, D. D. Anal. Chem. 2000, 72, 1242–1252.
50% MeOH
2...
24
0.00E+00
1.00E+07
2.00E+07
3.00E+07
4.00E+07
5.00E+07
6.00E+07
7.00E+07
8.00E+07
9 10 11 12 13 14 15 16 17 18 19 20 21 ...
0
20000000
40000000
60000000
80000000
100000000
120000000
9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27
Structur...
Preliminary Conclusions
• Three derivatizations produce generally the
same results
• Multivariate “design of experiment” a...
Acknowledgements
27
Walter C. Sumner
Memorial Foundation
G
C
D
Software
• OpenMS
• MSConvert
• R Statistical software
• Gaussian03W
• Marvin Sketch (ChemAxon)
• PyMOL
28
IDEAS
• Kanamori polymer to adsorb hydrophobic
species directly from wastewater; direct DESI
(MeOH) of marshmallow fragmen...
Summary of Theoretical Preamble
• 3° amine is protonated in acidic media
• Carboxamide moiety is more electrophilic
• Upon...
31
Nominal Mass
Probable structure (based on
m/z−𝟏𝟏𝟕
𝟏𝟒
+ 𝟏)
484 (Z=0) 27 carbon naphthenic acid
468 (Z=0) 26 carbon napht...
25.3 °
twist
41.7 °
twist
11 °
twist
4.215 Å
2.224 Å
4.055 Å
32
33
HOMO
LUMO
B3LYP 6-31G(d)
Prochain SlideShare
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A brand new method of analyzing organic contaminants in oil sands tailings pond waters

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A brand new method of analyzing organic contaminants in tailings pond waters! Miniaturizable, high-voltage, high potential. The oil sands industry will benefit from this.

Capillary electrophoresis-electrospray ionization-mass spectrometry technology for the analysis of naphthenic acids fraction compounds in oil sands process-affected waters.

Technical, peer-reviewed description of the optimized method: https://doi.org/10.1016/j.jes.2016.06.019

Publié dans : Sciences
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A brand new method of analyzing organic contaminants in oil sands tailings pond waters

  1. 1. Capillary electrophoresis-mass spectrometry technology for the analysis of naphthenic acid fraction compounds in oil sands process waters M.S. MacLennan, C. Tie, K.M. Peru, J.V. Headley, D.D.Y. Chen 1
  2. 2. Contents • Instrumentation setup • Sample preparation • Three “modes of attack” for NAs • Results workup 2
  3. 3. Flow-through Microvial Interface for CE-ESI-MS Maxwell, E. J.; Zhong, X.; Zhang, H.; van Zeijl, N.; Chen, D. D. Y. Electrophoresis 2010, 31, 1130–1137. 3
  4. 4. EDC-NHS Derivatization(s) of naphthenic acids 4 Hermanson, G. T. Bioconjugate Techniques; 2nd ed.; Elsevier Inc., 2008; p. 1323.
  5. 5. 5
  6. 6. Three modes of attack Capillary Zone Electrophoresis Field Amplified Sample Injection Polarity Switching Nonaqueous capillary electrophoresis Weak pH/solubility junction 6
  7. 7. Capillary Zone Electrophoresis (CZE) • All three derivatization mixtures • Capillary 50 μm i.d., coated with PEI(+) • Small sample plug injected hydrodynamically (0.5 psi, 10 sec) • Sandwiched between buffer (50% MeOH, 2% HCOOH) • Separation voltage -30 kV 7
  8. 8. EDC derivatization of NAs 8
  9. 9. EDC-NHS derivatization of NAs 9
  10. 10. 10 EDC-Sulfo-NHS derivatization of NAs
  11. 11. 11 C10 Z=0,-2 C11 Z=0,-2,-4 C12 Z=0,-2,-4 C13 Z=0,-2,-4 C14 Z=0,-2,-4 C15 Z=0,-2,-4 C16 Z=0,-2,-4
  12. 12. 12
  13. 13. 13
  14. 14. Field-Amplified Sample Injection (FASI) • Short plug of water introduced into the capillary (0.5 psi 10 sec) • Sample injected by applied voltage of +10 kV for 2 seconds • Electrophoretic separation carried out as per usual 14 Chien, R.-L.; Burgi, D. J. Chromatogr. 1991, 559, 141–152.
  15. 15. 15 Field-Amplified Sample Injection (FASI) EDC EDC-NHS EDC-Sulfo-NHS
  16. 16. 16
  17. 17. A. B. C. D. E. E. 17
  18. 18. 1.460 1.457 1.461 1.504 1.514 1.524 4 10 14 18 45 amu
  19. 19. A. B. C. D. E. E. 19
  20. 20. 20
  21. 21. Field Amplified Sample Injection with Polarity Switching (FASI-PSw) • Begin with FASI • Separate with -30 kV • At ~8.3 minutes, switch voltage to +30 kV and separate for 4 minutes • Switch polarity to -30 kV for 4 minutes • Decrease time to switch • 3 switches in total 21 Chien, R.-L.; Burgi, D. S. J. Chromatogr. A 1991, 559, 153–161.
  22. 22. 22
  23. 23. S EOF (+ESI)-MS 23 Weak pH/solubility gradient Britz-McKibbin, P.; Chen, D. D. Anal. Chem. 2000, 72, 1242–1252. 50% MeOH 2% Formic acid 48% water 90% MeOH 10% Formic acid 0% water
  24. 24. 24 0.00E+00 1.00E+07 2.00E+07 3.00E+07 4.00E+07 5.00E+07 6.00E+07 7.00E+07 8.00E+07 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 TotalIonCountforPeakofInterest Carbon number Structural distribution for naphthenic acids in Sigma-Aldrich Technical mixture Z=0 Z=-2 Z=-4 Z=-6 Z=-8
  25. 25. 0 20000000 40000000 60000000 80000000 100000000 120000000 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 Structural distribution for naphthenic acids in Sigma-Aldrich Technical mixture Z=0 Z=-2 Z=-4 Z=-6 Z=-8 25
  26. 26. Preliminary Conclusions • Three derivatizations produce generally the same results • Multivariate “design of experiment” and response surfaces for system optimization • Nonaqueous CE underivatized NAs • Analysis of native OSPW sample 26
  27. 27. Acknowledgements 27 Walter C. Sumner Memorial Foundation G C D
  28. 28. Software • OpenMS • MSConvert • R Statistical software • Gaussian03W • Marvin Sketch (ChemAxon) • PyMOL 28
  29. 29. IDEAS • Kanamori polymer to adsorb hydrophobic species directly from wastewater; direct DESI (MeOH) of marshmallow fragment • Chemometric analysis using alternate buffer compositions and pH. 29
  30. 30. Summary of Theoretical Preamble • 3° amine is protonated in acidic media • Carboxamide moiety is more electrophilic • Upon protonation: – 3° ammonium twists toward carboxamide – 3° ammonium bond lengths increase suggesting a possible neutral fragment loss of 45 amu 30
  31. 31. 31 Nominal Mass Probable structure (based on m/z−𝟏𝟏𝟕 𝟏𝟒 + 𝟏) 484 (Z=0) 27 carbon naphthenic acid 468 (Z=0) 26 carbon naphthenic acid 456 (Z=0,-2,-4) 25 carbon naphthenic acid 399 (Z=0,-2,-4) 21 carbon naphthenic acid 383 (Z=0,-2) 20 carbon naphthenic acid 369 (Z=0,-2,-4,-6) 19 carbon naphthenic acid 351 (Z=0,-2,-4,-6,-8) 18 carbon naphthenic acid 342 (Z=0,-2,-4,-6) 17 carbon naphthenic acid 328 (Z=0,-2,-4,-6) 16 carbon naphthenic acid 314 (Z=0,-2,-4,-6) 15 carbon naphthenic acid 299 (Z=0,-2,-4) 14 carbon naphthenic acid 285 (Z=0,-2,-4) 13 carbon naphthenic acid 271 (Z=0,-2,-4) 12 carbon naphthenic acid 257 (Z=0,-2,-4) 11 carbon naphthenic acid 244 (Z=0,-2) 10 carbon naphthenic acid 229 (Z=0) 9 carbon naphthenic acid 213 7 carbon naphthenic acid, one ring 129* Common fragment
  32. 32. 25.3 ° twist 41.7 ° twist 11 ° twist 4.215 Å 2.224 Å 4.055 Å 32
  33. 33. 33 HOMO LUMO B3LYP 6-31G(d)

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