Petroleum is undoubtedly the most complex natural mixture known, and its myriad chemical components offer an extraordinary challenge for even the most advanced analytical platforms. Since the introduction of Petroleomic methodologies over a decade ago, a more complete, molecular-level understanding of petroleum has begun to emerge. The use of high resolving power mass spectrometers has led the charge, but new technologies are required for isomer elucidation. Thus, ion mobility with mass spectrometry provides a much-needed structural component to the already complex world of petroleum compositional analysis: the potential for isomer resolution. In this work, we introduce new software (PetroOrg-Software ©) and methodologies that reveal crude oil composition, at the isomeric level, in an automated and chemically intelligent way.

1. ©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

2. ©2015 Waters Corporation 2
Presentation Overview
Data Handling & Discussion
Conclusions
Acknowledgements
Background & Introduction
Instrumentation & Methods
Spectra & Results

3. ©2015 Waters Corporation 3
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

4. ©2015 Waters Corporation 4
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: 1.32E5
T: FTMS + p APCI corona Full ms [100.00-1000.00]
100 200 300 400 500 600 700 800 900 1000
m/z
0
5
10
15
20
25
30
35
40
45
50
55
60
65
70
75
80
85
90
95
100
RelativeAbundance
458.37805
C33 H48 N1
-0.17799 ppm
126.30179
581.51239
C40 H69 32S1
1.61369 ppm
539.46518
C37 H63 32S1
1.26341 ppm
428.33117
C31 H42 N1
-0.01740 ppm
230.66370
400.29995
C29 H38 N1
0.17619 ppm
609.54385
C42 H73 32S1
1.79589 ppm
169.10114
C13 H13
-0.20911 ppm
370.25316
C27 H32 N1
0.63714 ppm
316.20606
C23 H26 N1
0.25327 ppm
653.60615
C45 H81 32S1
1.21870 ppm
697.66703
C48 H89 32S1
-1.31986 ppm
981.64640
C72 H85 32S1
9.92988 ppm
756.61156
854.00453
C67 H4 N1 32S1
-1.59983 ppm
886.69177
918.74726

5. ©2015 Waters Corporation 5
Background & Introduction :
Ion Mobility in Petroleum Analysis
 Use of ion mobility-mass spectrometry is relatively recent in petroleomics
– Drift tube ion mobility:
– TWIM:

6. ©2015 Waters Corporation 6
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?

7. ©2015 Waters Corporation 7
Instrumentation & Methods:
Mass Spectrometer
 SYNAPT G2-S HDMS instrument

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 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

9. ©2015 Waters Corporation 9
 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

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Spectra & Results:
Electrospray - VGO Hydrotreatment Effluent
Mobilogram

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Spectra & Results:
Electrospray - VGO Hydrotreatment Effluent

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Spectra & Results:
APPI – Safaniya Vacuum Residue
ML and DS spectra

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Spectra & Results:
ASAP – Boscan Vacuum Residue
50 oC
250 oC
350 oC
450 oC
550 oC
650 oC

14. ©2015 Waters Corporation 14
Spectra & Results:
ASAP – Boscan Vacuum Residue
50 oC

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Spectra & Results:
ASAP – Boscan Vacuum Residue
250 oC

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Spectra & Results:
ASAP – Boscan Vacuum Residue
350 oC

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Spectra & Results:
ASAP – Boscan Vacuum Residue
450 oC

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Spectra & Results:
ASAP – Boscan Vacuum Residue
550 oC

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Spectra & Results:
ASAP – Boscan Vacuum Residue
650 oC

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Data Handling & Discussion:
Ion Mobility Data in PetroOrg

21. ©2015 Waters Corporation 21
Data Handling & Discussion:
Ion Mobility Data in PetroOrg

22. ©2015 Waters Corporation 22
Data Handling & Discussion:
Ion Mobility Data in PetroOrg

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Data Handling & Discussion:
ESI(+) - VGO Hydrotreatment Effluent
40
20
10
0
30
DBE
10 20 30 40 50 60
N1
Carbon Number
Relative Abundance (% Total)
20
10
5
0
15
DriftTime(ms)
10 20 30 40 50 60
N1
Carbon Number
DBE

24. ©2015 Waters Corporation 24
Data Handling & Discussion:
APPI(+) – Safaniya Vacuum Residue
160
80
40
0
120
DriftTime
10 20 30 40 50 60
Carbon Number
S1
DBE

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Data Handling & Discussion:
APPI(+) – Safaniya Vacuum Residue
40
20
10
0
30
DBE
10 20 30 40 50 60
Carbon Number
S1
Relative Abundance (% Total)
S
S
S

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Data Handling & Discussion:
ASAP(+) – Boscan Vacuum Residue
250 oC
10 20 30 50 60
HC
DriftTime
160
80
40
0
120
DBE
40
Carbon Number

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Data Handling & Discussion:
ASAP(+) – Boscan Vacuum Residue
10 20 30 40 50 60
HC
Carbon Number
DriftTime
160
80
40
0
120
DBE
350 oC

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Data Handling & Discussion:
ASAP(+) – Boscan Vacuum Residue
10 20 30 40 50 60
HC
Carbon Number
DriftTime
160
80
40
0
120
DBE
450 oC

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Data Handling & Discussion:
ASAP(+) – Boscan Vacuum Residue
10 20 30 40 50 60
HC
Carbon Number
DriftTime
160
80
40
0
120
DBE
550 oC

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Data Handling & Discussion:
ASAP(+) – Boscan Vacuum Residue
160
80
40
0
120
DriftTime
10 20 30 40 50 60
HC
Carbon NumberDBE
650 oC

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Data Handling & Discussion:
ASAP(+) – Boscan Vacuum Residue
40
20
10
0
30
DBE
10 20 30 40 50 60
HC
Carbon NumberRelative Abundance (% Total)
Possible result
of fragmentation
Alkylated
parent ions
250 oC

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Relative Abundance (% Total)
Data Handling & Discussion:
ASAP(+) – Boscan Vacuum Residue
350 oC
Possible result
of fragmentation
Alkylated
parent ions
40
20
10
0
30
DBE
10 20 30 40 50 60
Carbon Number
HC

33. ©2015 Waters Corporation 33
Data Handling & Discussion:
ASAP(+) – Boscan Vacuum Residue
Relative Abundance (% Total)
450 oC
Possible result
of fragmentation
Alkylated
parent ions
40
20
10
0
30
DBE
10 20 30 40 50 60
HC
Carbon Number

34. ©2015 Waters Corporation 34
Data Handling & Discussion:
ASAP(+) – Boscan Vacuum Residue
Relative Abundance (% Total)
550 oC
Possible result
of fragmentation
Alkylated
parent ions
40
20
10
0
30
DBE
10 20 30 40 50 60
HC
Carbon Number

35. ©2015 Waters Corporation 35
Data Handling & Discussion:
ASAP(+) – Boscan Vacuum Residue
Relative Abundance (% Total)
650 oC
Possible result
of fragmentation
Alkylated
parent ions
40
20
10
0
30
DBE
10 20 30 40 50 60
HC
Carbon Number

36. ©2015 Waters Corporation 36
Data Handling & Discussion:
ASAP: In Agreement with the Literature
15 25 35 455
DBE 10
DBE 17
DBE 23
DBE 26
DBE 9
DBE 15
DBE 21
DBE 25
DBE 12
DBE 18
Carbon Number
15 25 35 455
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

37. ©2015 Waters Corporation 37
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

38. ©2015 Waters Corporation 38
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

39. ©2015 Waters Corporation 39
Acknowledgements
Thank you
for your attention!