ion mobility petroleomics: towards isomeric compositional space elucidation via new software and...

©2015 Waters Corporation 1

Ion Mobility Petroleomics: Towards Isomeric Compositional Space

Elucidation via New Software and Methods

Eleanor Riches1; Priscila Lalli2; Ryan P. Rodgers2, 3; Yuri Corilo2, 3 1Waters Corporation, Wilmslow, UK;

2National High Magnetic Field Laboratory, Tallahassee, FL; 3Future Fuels Institute, Tallahassee, FL

62nd ASMS Conference

Baltimore, 18th June 2014


Presentation Overview

Data Handling & Discussion

Conclusions

Acknowledgements

Background & Introduction

Instrumentation & Methods

Spectra & Results


Background & Introduction: State of the Art

Petroleum samples provide one of the biggest challenges for scientists in the field of analytical chemistry

5 3 8 18 10 75 12 355 15 8347 20 36.6 x 104

25 36.7 x 106

30 41.1 x 108

35 49.3 x 1010

40 62.4 x 1012

45 82.2 x 1014

60 221.5 x 1020

80 1056 x 1028

100 5920 x 1038

Carbon Number

Number of Isomers

Fractions

Gasoline

Diesel

VGO

VR


Background & Introduction : State of the Art

The incumbent mass spectrometric technology for petroleomics analyses is FTICR-MS – Resulting in some of the most information-rich data sets

ASAP-S-50-60-1006_3 #1-15 RT: 0.01-6.81 AV: 15 NL: 1.32E5T: FTMS + p APCI corona Full ms [100.00-1000.00]

100 200 300 400 500 600 700 800 900 1000m/z

0

5

10

15

20

25

30

35

40

45

50

55

60

65

70

75

80

85

90

95

100

Rel

ativ

e A

bund

ance

458.37805C33 H48 N1

-0.17799 ppm

126.30179

581.51239C40 H69 32S1

1.61369 ppm

539.46518C37 H63 32S1

1.26341 ppm

428.33117C31 H42 N1

-0.01740 ppm

230.66370

400.29995C29 H38 N1

0.17619 ppm

609.54385C42 H73 32S1

1.79589 ppm

169.10114C13 H13

-0.20911 ppm

370.25316C27 H32 N1

0.63714 ppm

316.20606C23 H26 N1

0.25327 ppm

653.60615C45 H81 32S1

1.21870 ppm

697.66703C48 H89 32S1

-1.31986 ppm

981.64640C72 H85 32S1

9.92988 ppm

756.61156

854.00453C67 H4 N1 32S1

-1.59983 ppm886.69177

918.74726


Background & Introduction : Ion Mobility in Petroleum Analysis

Use of ion mobility-mass spectrometry is relatively recent in petroleomics

– Drift tube ion mobility:

– TWIM:


Background & Introduction : The Focus of the Study

The questions we asked: – What complementary information can ion mobility – mass spectrometry offer

to petroleum analysis?

– How do we unlock the multidimensional petroleomics data acquired using SYNAPT ion mobility mass spectrometry?


Instrumentation & Methods: Mass Spectrometer

SYNAPT G2-S HDMS instrument


ElectroSpray Ionization (ESI+) – Vacuum gas oil (VGO) hydrotreatment feed and effluent

samples provided by collaborators from IFP Energies nouvelle (Solaize, France)

– Solutions were prepared as 5 mg/mL in 1:1 (v/v) toluene:methanol with 0.1% formic acid

– Sample solutions were infused using a Harvard syringe pump at a flow rate of 10 µL/min

Atmospheric Pressure Photoionization (APPI+)

– Vacuum residue samples with different geographical origins were provided by collaborators from IFP Energies nouvelle (Solaize, France)

– Solutions were prepared as 2 mg/mL in 1:1 (v/v) toluene:methanol with 0.1% formic acid

– Sample solutions were infused using a Harvard syringe pump at a flow rate of 10 µL/min

Instrumentation & Methods: ESI & APPI Analyses


Atmospheric Solids Analysis Probe (ASAP+) ionization – Atmospheric Solids Analysis Probe: thermal desorption followed by classical APCI – Boscan vacuum residue (≥350 oC) was provided by a collaborator from IFP Energies nouvelle (Solaize, France)

Samples were analysed by ASAP using a stepwise temperature ramp – T0 min = 50 oC Start acquisition – T0.5 min = 50 oC Insert probe – T1.0 min = 250 oC – T2.0 min = 350 oC – T3.0 min = 450 oC – T4.0 min = 550 oC – T5.0 min = 650 oC – T6.0 min = 650 oC Stop acquisition

Instrumentation & Methods: ASAP Analyses


Spectra & Results: Electrospray - VGO Hydrotreatment Effluent

Mobilogram


Spectra & Results: Electrospray - VGO Hydrotreatment Effluent


Spectra & Results: APPI – Safaniya Vacuum Residue

ML and DS spectra


Spectra & Results: ASAP – Boscan Vacuum Residue

50 oC

250 oC

350 oC

450 oC

550 oC 650 oC



50 oC



250 oC



350 oC



450 oC



550 oC



650 oC


Data Handling & Discussion: Ion Mobility Data in PetroOrg


Data Handling & Discussion: ESI(+) - VGO Hydrotreatment Effluent

40

20

10

0

30

DB

E

10 20 30 40 50 60

N1

Carbon Number

Relative Abundance (% Total)

20

10

5

0

15

Drif

t Tim

e (m

s)

10 20 30 40 50 60

N1

Carbon Number

DBE


Data Handling & Discussion: APPI(+) – Safaniya Vacuum Residue

160

80

40

0

120

Drif

t Tim

e

10 20 30 40 50 60

Carbon Number

S1

DBE


Data Handling & Discussion: APPI(+) – Safaniya Vacuum Residue

40

20

10

0

30

DB

E

10 20 30 40 50 60

Carbon Number

S1


S

S

S


Data Handling & Discussion: ASAP(+) – Boscan Vacuum Residue

250 oC

10 20 30 50 60

HC

Drif

t Tim

e

160

80

40

0

120

DBE

40

Carbon Number



10 20 30 40 50 60

HC

Carbon Number

Drif

t Tim

e

160

80

40

0

120

DBE

350 oC



10 20 30 40 50 60

HC

Carbon Number

Drif

t Tim

e

160

80

40

0

120

DBE

450 oC



10 20 30 40 50 60

HC

Carbon Number

Drif

t Tim

e

160

80

40

0

120

DBE

550 oC



160

80

40

0

120

Drif

t Tim

e

10 20 30 40 50 60

HC

Carbon Number DBE

650 oC



40

20

10

0

30

DB

E

10 20 30 40 50 60

HC

Carbon Number Relative Abundance (% Total)

Possible result of fragmentation

Alkylated parent ions

250 oC




350 oC



40

20

10

0

30

DB

E

10 20 30 40 50 60

Carbon Number

HC




450 oC



40

20

10

0

30

DB

E

10 20 30 40 50 60

HC

Carbon Number




550 oC



40

20

10

0

30

DB

E

10 20 30 40 50 60

HC

Carbon Number




650 oC



40

20

10

0

30

DB

E

10 20 30 40 50 60

HC

Carbon Number


Data Handling & Discussion: ASAP: In Agreement with the Literature

15 25 35 45 5

DBE 10

DBE 17

DBE 23

DBE 26

DBE 9

DBE 15

DBE 21

DBE 25

DBE 12

DBE 18

Carbon Number 15 25 35 45 5

HC Class

Double Bond Equivalents vs. C# IRMPD APPI(+) FT-ICR MS.

Total de-alkylation revealing the core structures

DBE 20

DBE 7

DBE 14

Ref: Podgorski, D. C., et al., Energy & Fuels, 2013, 27, pp 1268 - 1276


Conclusions

Novel software tools help to visualize, interact with, and process ion mobility-mass spectrometry data for comprehensive, petroleomics-specific data analysis

On the road towards isomeric compositional space elucidation, ion mobility-mass spectrometry can help to…

— Offer an additional orthogonal dimension of separation

— Deconvolute isomeric species in the ion mobility dimension

— Simplify the analysis of very complex samples

— Map the compositional space of petroleum samples

— Characterise the shapes and/or sizes of materials


Acknowledgements

Waters colleagues: Kirsten Craven, Adam Parkinson, Neil Gardner

Collaborators: Jérémie Ponthus, Jérémie Barbier and Laure Boursier, IFP Energies nouvelles, France

Yuri E. Corilo: PetroOrg development and collaboration


Acknowledgements

Thank you for your attention!

ion mobility petroleomics: towards isomeric compositional space elucidation via new software and...

Science

waters corporation

ion mobility petroleomics

c67 h4 n1 32s1

c42 h73 32s1

c45 h81 32s1

c37 h63 32s1

c48 h89 32s1

c40 h69 32s1