Ion Mobility Petroleomics: Towards Isomeric Compositional Space Elucidation via New Software and...
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Transcript of 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
©2015 Waters Corporation 2
Presentation Overview
Data Handling & Discussion
Conclusions
Acknowledgements
Background & Introduction
Instrumentation & Methods
Spectra & Results
©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
©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: 1.32E5T: 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
©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:
©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?
©2015 Waters Corporation 8
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
©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
©2015 Waters Corporation 10
Spectra & Results: Electrospray - VGO Hydrotreatment Effluent
Mobilogram
©2015 Waters Corporation 13
Spectra & Results: ASAP – Boscan Vacuum Residue
50 oC
250 oC
350 oC
450 oC
550 oC 650 oC
©2015 Waters Corporation 23
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
©2015 Waters Corporation 24
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
©2015 Waters Corporation 25
Data Handling & Discussion: APPI(+) – Safaniya Vacuum Residue
40
20
10
0
30
DB
E
10 20 30 40 50 60
Carbon Number
S1
Relative Abundance (% Total)
S
S
S
©2015 Waters Corporation 26
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
©2015 Waters Corporation 27
Data Handling & Discussion: ASAP(+) – Boscan Vacuum Residue
10 20 30 40 50 60
HC
Carbon Number
Drif
t Tim
e
160
80
40
0
120
DBE
350 oC
©2015 Waters Corporation 28
Data Handling & Discussion: ASAP(+) – Boscan Vacuum Residue
10 20 30 40 50 60
HC
Carbon Number
Drif
t Tim
e
160
80
40
0
120
DBE
450 oC
©2015 Waters Corporation 29
Data Handling & Discussion: ASAP(+) – Boscan Vacuum Residue
10 20 30 40 50 60
HC
Carbon Number
Drif
t Tim
e
160
80
40
0
120
DBE
550 oC
©2015 Waters Corporation 30
Data Handling & Discussion: ASAP(+) – Boscan Vacuum Residue
160
80
40
0
120
Drif
t Tim
e
10 20 30 40 50 60
HC
Carbon Number DBE
650 oC
©2015 Waters Corporation 31
Data Handling & Discussion: ASAP(+) – Boscan Vacuum Residue
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
©2015 Waters Corporation 32
Relative Abundance (% Total)
Data Handling & Discussion: ASAP(+) – Boscan Vacuum Residue
350 oC
Possible result of fragmentation
Alkylated parent ions
40
20
10
0
30
DB
E
10 20 30 40 50 60
Carbon Number
HC
©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
DB
E
10 20 30 40 50 60
HC
Carbon Number
©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
DB
E
10 20 30 40 50 60
HC
Carbon Number
©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
DB
E
10 20 30 40 50 60
HC
Carbon Number
©2015 Waters Corporation 36
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
©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
©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