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ION MOBILITY & PETROORG SOFTWARE: NOVEL TECHNIQUES FOR PETROLEOMICS INVESTIGATIONS

Eleanor Riches1, Yuri E Corilo2,3, Ryan P. Rodgers2,3, Michael J O’Leary4, Douglas Stevens4,

1. Waters Corporation, Wilmslow, SK9 4AX, UK; 2. National High Magnetic Field Laboratory, Florida State University, Tallahassee, Florida, 32310-4005; 3. Future Fuels Institute, Tallahassee, Florida, 32310-4005; 4. Waters Corporation, Milford, MA, 01757

INTRODUCTION

Petroleum is one of the most complex natural

substances, which provides one of the biggest

challenges any analytical chemist will ever encounter.

This is due, in no small part, to the huge number of

possible isomers that could be present in such complex

samples. After the introduction of Petroleomics

methods, over a decade ago, the complexity of

petroleum starts to be revealed.1

The incumbent mass spectrometric technique of choice

for petroleum analyses is FTICR-MS,2 which gives rise to

some of the most information-rich data sets possible.

However, interest in using ion mobility-mass

spectrometry (IM-MS) for petroleum investigations has

been apparent since the mid-2000s, when initial studies

using classical drift tubes took place.3,4 Subsequently,

there has been an increasing focus on the application of

travelling wave ion mobility-MS (TWIM-MS) for

petroleomics studies.5,6,7

In this work, we will show IM-MS coupled with new

software (PetroOrg Software©)8 and methodologies that

allow the determination of the crude oil composition,

within the isomeric level, in an automated and

chemically intelligent way.

METHODS

Sample Preparation

Boscan VGO sample was supplied by a collaborator from IFPEN

(Solaize, France). A solution was prepared at a concentration of

1.0 mg/mL in 1:1 MeOH:Toluene (v/v)

MS Conditions (IMS-MS)

MS system: SYNAPT G2-Si HDMS

Ionization mode: ASAP+

Analyser: High Resolution mode (40K resolution)

Corona current: 20 A

Source temp: 120 oC

Desolvation temp: 150—650 oC (see Table 1)

Sampling cone: 35.0 V

Mass range: m/z 50 – 1200

Wave velocity: 1200 m/s

Wave height: 40 V

LockSpray solution: Leucine enkephalin

LockSpray mass: m/z 556.2766

Data were acquired using MassLynx v4.1, and processed using

DriftScope software version 2.7 (Waters Corporation), and

PetroOrg software version 7 (Omics LLC, Tallahassee, FL)

CONCLUSIONS

ASAP data acquired using the SYNAPT ion mobility mass

spectrometer were easily uploaded into PetroOrg

Data processing revealed qualitative information about

the sample at the molecular level.

The combination of high resolution ion mobility data

acquisition and PetroOrg data processing enabled access

to the isomeric components of petroleum samples.

Structural information gained using this approach was in

good agreement with the literature.1

Acknowledgments

Great thanks goes to Jérémie Ponthus, IFP energies nouvelles, Solaize,

France, for providing the samples used in this work.

References

1.Podgorski, D.C.; Corilo, Y.E.; Nyadong, L.; Lobodin, V.V.; Robbins,

W.K.; McKenna, A.M.; Marshall, A.G.; Rodgers, R.P., Energy & Fuels

2013, 27, 1268-1276.

2.Rodgers, R.P.; Schaub, T.M.; Marshall, A.G., Anal. Chem. 2005, 77, 21A

- 27A.

3.Becker, C.; Qian, K.; Russell, D.H., Anal. Chem. 2008, 80, 8592-8597.

4.Fernandez-Lima, F. A.; Becker, C.; McKenna, A.M.; Rodgers, R.P.;

Marshall, A.G.; Russell, D.H., Anal. Chem. 2009, 81, 9941-9947.

5.Ahmed, a.; Cho, Y. J.; No, M.; Koh, J.; Tomczyk, N.; Giles, K.; Yoo, J.S.;

Kim, S., Anal. Chem. 2011, 83, 77-83.

6.Fasciotti, M.; Lalli, P.M.; Klitzke, C.F.; Corilo, Y.E.; Pudenzi, M.A.;

Pereira, R.C.L.; Bastos, W.; Daroda, R.J.; Eberlin, M.N., Energy & Fuels

2013, 27, 7277-7286.

7.Wu, C.; Qian, K.; Walters, C.C.; Mennito, A., Int. J. Mass

Spectrom.2014, http://dx.doi.org/10.1016/j.ijms.2014.08.019

8.Yuri E. Corilo, © PetroOrg Software, Florida State University, All rights

reserved, http://software.petroorg.com

RESULTS & DISCUSSION

Figure 7. Plots of Carbon Number versus DBE for the hydrocar-

bon (HC) class at each temperature. The relative abundance is indicated by the colour scale. Regions corresponding to frag-

ment ions (dotted red line) and alkylated precursor ions (red oval) are highlighted at each temperature.

Figure 1 shows a schematic of the SYNAPT G2-Si HDMS

ion mobility instrument used in this study, and Figure 2

shows the Atmospheric Solids Analysis Probe (ASAP) ion

source.

Figure 5 shows an image of the data import screen in PetroOrg

software. In this data import screen we can see the full mass

spectrum on the lower pane, a two-dimensional view of the ion

mobility data in the middle pane, and the chromatogram in the

upper pane (in this case we can see the thermal desorption

profile from the ASAP analysis). The red square superimposed

on the image highlights the button used to specifically import

unique Waters high resolution ion mobility data.

Figure 6 shows examples of the unique plots available in the

PetroOrg software for Waters ion mobility data. Here we can

see Carbon Number plotted against Drift Time. The colour

scale represents DBE—the closer the colour is to the red end of

the spectrum, the higher the DBE value. If we consider a

single carbon number class, we can see that higher DBE values

have shorter drift times. This provides empirical evidence that

species with higher DBE values, which are therefore more

aromatic, have more compact structures.

Figure 7 shows more typical Carbon Number versus DBE plots.

In this figure we can see two distinct regions that become

more apparent at higher temperatures. These regions

correspond to fragment ions and intact alkylated precursor

ions, thus providing valuable structural information.

Time

(mins)

Temperature

(oC) Action

0.00 50 Start acquisition

0.50 50 Insert probe

1.00 250

2.00 350

3.00 450

4.00 550

5.00 650

6.00 650 Stop acquisition

Table 1. Temperature ramp applied to the ASAP in source

Figure 1. A schematic of the SYNAPT® G2-Si HDMS™ instrument, with

travelling wave ion mobility functionality.

Figure 2. The Atmospheric Solids

Analysis Probe (ASAP).

Within the DriftScope ion mobility software it is possible to

select and isolate regions or masses of interest. A preliminary

review of the data in DriftScope revealed many components

that had species separated in the ion mobility dimension.

Figure 3 illustrates one such example.

Figure 4 shows the ASAP thermal desorption profile for the

Boscan sample. Both the TIC and the spectrum produced at

each temperature are illustrated. This allows us to observe the

change in ion distribution over increasing temperature but

does not allows us to identify any key components or classes.

Figure 5. SYNAPT HDMS ion mobility data prior to being pro-

cessed in PetroOrg software.

Figure 3. A: Two selected mass spectral peaks have very

broadly distributed drift times., which suggests mobility re-solved isomers. In three dimensional views, B: viewing the

Mass (m/z) axis we see only two resolved masses, C: viewing the Drift Time (ion mobility) axis we see multiple different

species.

Figure 4. The thermal desorption Total Ion Chromatogram

(TIC) and corresponding mass spectrum for each temperature.

Figure 6. Plots of Carbon Number versus Drift Time for the Hy-

drocarbon class (HC) at each temperature. DBE is indicated by the colour scale.

Figure 8. Core structures revealed as a result of Infrared Multi-

Photon Dissociation (IRMPD) followed by analysis using positive ion mode APPI coupled to FT-ICR MS. [Image shown with kind permis-

sion from the authors of reference 1.]

Previously published work,1 illustrated in Figure 8, which used a some-

what different mass spectral approach, is in good agreement with the

findings of our analysis. The primary difference being that, by using

ASAP, we were able to observe both the core structures as a result of

fragmentation and the intact alkylated precursor ions.