Meeting the Petrochemical Challenge with

Separation Science and Mass Spectrometry

Burlington House 14 November 2014

GOLD Sponsors

SILVER Sponsors

PROGRAMME

09.00 Registration with Tea/Coffee

09.45 Welcome & Opening Remarks (John Langley, University of Southampton)

Session Chair: Tom Lynch (BP, Pangbourne)

10.00 Philip Marriott (Monash University): Multidimensionality in Gas Chromatography - Revealing

Molecular Information from Complex Samples

10.50 Mark Barrow (University of Warwick): Ultra-High Resolution MS

11.10 Alessando Vetere (Max Planck Institute): FAIMS-FTMS: A New Approach to Unravelling Crude Oil

11.30 Kirsten Craven (Waters Corporation): The Potential and Possibilities of Mass Spectrometry with Ion

Mobility for the Analysis of Petroleum and Polymeric Materials

11.50 Laura McGregor (Markes International) - Gold Sponsor Presentation: Enhanced Crude Oil

Fingerprinting by GC x GC-TOF MS with Soft Electron Ionisation

12.10 Vincent Jespers (Thermo Scientific) - Gold Sponsor Presentation: Developments in Orbitrap

Technology

12.30 Lunch & Exhibition

Session Chair: John Langley (University of Southampton)

13.30 Jürgen Wendt LECO - Gold Sponsor Presentation: High Resolution GC-TOF MS for Petrochemical

Applications

13.50 Didier Thiebaut (ESPCI, Paris): SFC Based Applications in the Petroleum Related Industry

14.40 Sophie Moore (University of Lincoln): Fuel Compatible Marking Systems

15.00 Waraporn Ratsameepakai (University of Southampton): Fatty Acid Methyl Esters (FAMEs) Issues

and Hyphenated Mass Spectrometry Solutions

15.20 Tea/Coffee

15.40 Caitlyn Da Costa (University of Loughborough): The Application of Desorption Electrospray

Ionisation Hyphenated with Ion Mobility-Mass Spectrometry for the Analysis of Oil and Oil Additives

16.00 Tom Lynch (BP, Pangbourne): Solving Problems with Hyphenation

16.50 Closing Remarks

16.55 Meeting Close

17.00 Cheese and Wine Reception

Meeting the Petrochemical Challenge with Separation Science and Mass Spectrometry

Abstracts & Biographies

Multidimensionality in Gas Chromatography: Revealing Molecular Information from Complex Samples

Philip Marriott (Australian Centre for Research on Separation Science, School of Chemistry, Monash

University, Australia)

Abstract

Petrochemicals analysis continues to be a major interest area due to the sheer complexity of the sample. In a

crude oil sample, nature has contrived to present perhaps the most difficult separation task for the analyst;

in down-stream products, the legacy of the initial sample’s complexity may still remain. This is a fertile

ground for the analyst to develop innovative and powerful separation solutions, but we are far from

accomplishing the goal of having a method that can separate all components of interest. This challenge

exercises the best capabilities of the analyst.

We have contributed a number of new approaches to overall sample ‘global profiling’, along with strategies

for sampling specific regions of a mixture to provide a best-case separation goal. These approaches are

based on well-established multidimensional gas chromatography (MDGC) and newer comprehensive two-

dimensional GC (GC × GC) methods, however we are interested in pushing these techniques to the limit of

separation power by integrating even further dimensions of separations. [1] We use various multiple

sampling strategies incorporating a Deans switch, from a 1D column to a 2D column, supported by cryogenic

zone compression and fast modulation to provide good efficiency for target sample analysis. This was

recently demonstrated for oxygenated component identification in a thermally stressed algae-derived jet

fuel product. A 1D GC-MS method was unable to identify the required components. [2] A similar approach

was used for high sulfur oil shale samples. [3]

A further advanced mode that we call hybrid GC × GC-MDGC, functions as an on-line matrix clean-up method,

or allows unique profiling of target chemical classes in ways never before possible. [4]

Since GC is as much about separation as identification (and best identification normally starts with best

separation), we are interested in applying MDGC with both mass spectrometry and NMR analysis, so that the

ultra-high chemical separation along with the two premier spectrometry characterisation tools of MS and

NMR can provide added structural molecular assignment. NMR suffers from poor sensitivity, but we

optimise injected sample quantity, the number of repeat injections, and NMR sensitivity to advance our

work. [5]

Literature

[1]. S.-T. Chin, P.J. Marriott. Multidimensional Gas Chromatography Beyond Simple Volatiles Separation

Chemical Communications, 50 (2014) 8819-8833.

[2]. B. Mitrevski, R. Webster, P. Rawson, D. Evans, H.-K. Choi, P.J. Marriott. Multidimensional gas

chromatography of oxidative degradation products in algal-derived fuel oil samples using narrow heartcuts

and rapid cycle times

Journal of Chromatography A; 1224 (2012) 89-96.

[3]. M. W. Amer, B. Mitrevski, W.R. Jackson, A.L. Chaffee, P.J. Marriott. Multidimensional and

Comprehensive Two-Dimensional Gas Chromatography of Dichloromethane Soluble Products from a High

Sulfur Jordanian Oil Shale. Talanta 120 (2014) 55–63.

[4]. B. Mitrevski, P.J. Marriott. A novel hybrid comprehensive two-dimensional – multi-dimensional gas

chromatography for precise, high resolution characterisation of multicomponent samples. Analytical

Chemistry, 84 (2012) 4837−4843.

[5]. G.T. Eyres, S. Urban, P.D. Morrison, P.J. Marriott. Application of microscale-preparative multidimensional

gas chromatography with nuclear magnetic resonance for identification of pure methylnaphthalenes from

crude oils. Journal of Chromatography A, 1215 (2008) 168-176.

Biography

http://chem.monash.edu/staff/marriott/index.html

Professor Marriott obtained his PhD from LaTrobe University, Melbourne. He undertook postdoctoral

research at the University of Bristol, UK, in the Organic Geochemistry Group. Following this, his first

academic appointment was at the National University of Singapore, School of Chemistry.

After 5 years in Singapore, he returned to Australia, first to the Royal Melbourne Institute of Technology

(RMIT University).

In 2010, he moved to his present position at Monash University, Melbourne. He received an Australian

Research Council Discovery Outstanding Researcher Award in 2013.

Through the Australian Academy of Science, he has had extended professional visits to China and Portugal.

He was recipient of a World Class University Distinguished Professorship under the Korean National Research

Foundation.

His primary research is in gas chromatography and mass spectrometry, specifically in comprehensive 2D GC

and multidimensional GC, with mass spectrometry, covering fundamental methods development and a

broad applications base.

Professor Marriott has published 320 research papers and book chapters.

A Closer Look at Petroleum using Ultrahigh Resolution Mass Spectrometry

Mark P. Barrow (Department of Chemistry, University of Warwick, UK)

Abstract

The characterization of petroleum at a molecular level has been termed “petroleomics.” Usage of ultrahigh

resolution mass spectrometry, particularly Fourier transform ion cyclotron resonance (FTICR) mass

spectrometry, makes it possible to resolve the tens of thousands of components present within complex

mixtures such as petroleum, leading to a number of advances. Coupling with electrospray ionization (ESI)

has afforded the ability to characterize the polar components of petroleum, whilst other ionization methods,

such as atmospheric pressure photoionization (APPI) and atmospheric pressure chemical ionization (APCI),

amongst others, can be used for investigating the less polar components.

Applications at the University of Warwick include the characterization of crude oils and of water samples

associated with the oil sands industry in the Athabasca region of Alberta, Canada. Exposure of crude oil to

light has been shown to result in photooxidation, particularly with respect to heteroatom-containing

components with a sample, with potential significance for acidity and solubility in water. Characterization of

environmental water samples and of oil sands process water (OSPW) samples has shown that it is not only

possible to differentiate between natural and industrial origins, but also between different oil sands

companies. Coupling of chromatographic methods, such as gas chromatography (GC), with FTICR mass

spectrometry provides additional information, including the potential to determine contributions from

isomers. The performance and versatility of FTICR mass spectrometry make it well-suited to the

characterization of petroleum and other complex mixtures.

Biography

Dr Mark P. Barrow is a Senior Research Fellow at the University of Warwick. Since 2000, his research has

primarily focused upon the study of petroleum-related complex mixtures using high field Fourier transform

ion cyclotron resonance (FTICR) mass spectrometry. In particular, this has involved usage of 9.4 T BioAPEX II

and 12 T solariX FTICR mass spectrometers. Dr Barrow’s research entails collaborations with the petroleum

industry and Environment Canada, amongst others. He serves as a reviewer for approximately twenty

journals and for various British, American, and Canadian funding bodies, as well as being a member of the

Royal Society of Chemistry (RSC), the British Mass Spectrometry Society (BMSS), the American Society for

Mass Spectrometry (ASMS), and the Energy Institute (EI).

FAIMS-FTMS: A New Approach to Unravelling Crude Oil

Alessandro Vetere, Wolfgang Schrader (Max-Planck-Institut für Kohlenforschung, Kaiser-Wilhelm-Platz 1,

45470 Mülheim an der Ruhr, Germany)

Abstract

The usage of crude oil e.g. as chemical feedstock or for purposes of energy retrieval is indivisibly linked with

a variety of problems. These include oil being spilled into the environment or pipeline clogging. Feasible

solutions to these problems are still to be found, or respectively the underlying processes understood.

Therefore a thorough and detailed understanding of the constituents of crude oils is desirable.

While highly resolving separation techniques such as 2-dimensional GC can – especially when combined with

mass spectrometric methods – provide detailed information also for isomeric compounds, these methods

are often limited to only small portions of the sample. This limitation could be overcome by employing a

combination of ultra-high resolution mass spectrometry and adequate separation techniques like ion

mobility.

FT-mass spectrometry, when making use of different ionization techniques, can cover all ranges of polarity

and volatility found in crude oils. The complexity of the sample and the problem of distinguishing between

isomeric compounds are here addressed by hyphenation to a differential ion mobility spectrometer (FAIMS)

which is further on optimized for a better resolution as well as for the implementation of additional

ionization techniques as Atmospheric Pressure Photo-Ionization.

Biography

Studies in chemistry from 2001 at the University of Münster, Germany

Graduation in analytical chemistry in 2012 under the supervision of Prof. Dr Jan T. Andersson focusing on

chromatographic separations of crude oils, with an emphasis on dibenzothiophenes. Title of the thesis:

“Analysis of aromatic sulfoxides by liquid chromatographic and NMR-spectroscopic methods”

Since 2013 PhD Student at the Max-Planck-Institute for Coal Research under the supervision of PD Dr

Wolfgang Schrader. Main topic of interest is the development of hyphenated techniques for the mass

spectrometric analysis of crude oil. Special focusses are on ligand exchange chromatography and differential

ion mobility coupling.

The Potential and Possibilities of Mass Spectrometry with Ion Mobility for the Analysis of Petroleum and

Polymeric Materials

Kirsten Craven (Waters Corporation, Wilmslow, UK)

Abstract

The complexity of oil and polymer samples offers a significant challenge to the analytical chemist, requiring a

range of analytical techniques to fully characterise them. Currently, the mass spectrometric instruments of

choice for complex samples are FTICR-MS and ToF, due to their high mass resolution capabilities and mass

range. However, exact mass data alone cannot always fully characterise a sample. Coupling ion mobility

with QTof MS offers an additional, orthogonal mode of separation, and can also provide information about

an ion’s size and shape.

Travelling wave ion mobility separations coupled with quadrupole time-of-flight (QTof) mass spectrometry

provide unique capabilities for characterisation of complex samples. This presentation will introduce the

technology within Waters SYNAPT G2-Si and the potential of ion mobility separations. Software for ion

mobility data interpretation, the simplification of data that can be achieved and structural elucidation

possibilities will be discussed.

Biography

Kirsten studied Chemistry and Analytical Science at the University of Birmingham, and graduated in 2003.

After graduating Kirsten worked for two large international companies, Ineos and SGS, as an Analytical

Scientist.

Immediately before joining Waters she worked for Unilever at their R&D site in the north of England, UK, as

a perfume analyst. As part of this role she was involved in transferring some their analytical methods and

delivering training in India. Kirsten started working for Waters in 2011 as an Application Specialist in the

Chemical Materials Business Operations group. In this role she is working with ACQUITY UPLC, Xevo bench

top Time of Flight and SYNAPT with ion mobility technologies to create system solutions for the Chemical

Materials industry. Kirsten’s current primary focus is to investigating how Waters’ high resolution MS

technologies can help the polymer industry meet their objectives.

SFC Based Applications in the Petroleum Related Industry

Didier Thiébaut (CNRS UMR 8231 Chimie Biologie Innovation Laboratoire Sciences Analytiques,

Bioanalytiques et Miniaturisation, ESPCI-ParisTech, France)

Abstract

In a tense global energetic context, petroleum industry has to face the challenge of upgrading heavier cuts or

converting coal derived liquids into valuable products, like diesel fuel. Therefore, to reach for the

specifications of final fuels before use and to improve the processes, a detailed characterization of feeds and

products is required during all conversion steps for evaluating their effectiveness. Owing to the high

complexity of the matrices to be investigated, the implementation of very efficient chromatographic

techniques is mandatory to reach for the highest selectivity and resolution capabilities.

This presentation will focus on Supercritical Fluid Chromatography implementation for hydrocarbon group

separation. Application to various cuts or fractions will be presented, including vacuum distillates, biofuels

and additives. The benefits of on-line hyphenation of SFC steps prior to GC x GC and /or selective detection

will be discussed. Promising features of SFC x SFC will be presented too despite the experimental complexity.

Biography

Senior Research Scientist at the French National Research Center (CNRS), UMR 8231 Chimie Biologie

Innovation Laboratoire Sciences Analytiques, Bioanalytiques et Miniaturisation, ESPCI ParisTech, France.

Research topics:

1. separation techniques including Supercritical Fluid Chromatography (SFC), Gas Chromatography (GC)

and Liquid Chromatography (LC)

2. GC on a chip and stationary phases for GC on a chip

3. extraction and sample preparation techniques and informative and selective detectors (MS, FTIR,

AED, SCD, NCD, ELSD …).

4. Fast and comprehensive separation techniques (during the last 10 years):

GC x GC and its hyphenation to GC, LC and SFC, LC x LC and SFC x SFC for the detailed analysis of very

complex samples such as oil samples (petroleomics), lipids (lipidomics), plant extracts, waste water.

Publications and conferences:

More than 90 publications, 3 books and one patent, more than 40 oral communications in international

symposium.

Professional Memberships, Symposium and Reviewing

President of "Francophone Association of Separation Sciences” (AfSep) and of the Steering Committee of

European Society for Separation Sciences (EuSSS), Member of national Academy of Pharmacy.

Fuel Compatible Marking Systems

Sophie Moore1, Mark Baron1 and Nicholas Meakin2 (School of Life Sciences, University of Lincoln, UK; Cipher

Pte Ltd, Singapore)

Abstract

Fuel fraud costs countries hundreds of millions of pounds annually. To combat this fuel fraud, chemical

markers are added to hydrocarbon fuels in order to enable their unique identification and to differentiate

between subsidised, non-subsidised and taxed fuel. Many markers currently in use can be removed by

laundering techniques; which include acid/alkali stripping and solid adsorbents such as charcoal and clay.

This allows subsidised fuel to be illegally traded as taxed fuel, resulting in lost revenue. Alternative ‘launder

resistant’ Forensic markers are required to facilitate prevention of fuel fraud and ensure specific fuels are

only used for their intended purpose.

Research is being conducted into the development of a Forensic marking system using substances that show

a range of chemical and physical properties compatible with diesel fuels. Substances occurring naturally in

fuels have been extracted and investigated using a developed solid phase extraction method to gain an

insight and understanding of the effects of common laundering techniques on different fuel components.

Substances structurally similar to those already present are being explored as potential marker compounds.

Gas Chromatography-Mass Spectrometry is ideal for diesel analysis and marker detection and so this is

proposed as the core analytical technique for the chemical identification of volatile and semi-volatile marker

compounds in diesel.

Biography

I am currently a PhD Research Student at the University of Lincoln. I graduated from my undergraduate

degree, BSc (Hons) Forensic Science, in 2010 and went on to complete an MSc by research in Analytical

Chemistry in 2012. I have just begun the third and final year of my PhD with the focus of my research being

alternative forensic marking systems for the fuel industry. My work involves the adaption of extraction

techniques for the characterisation of diesel fuels and the investigation into various common laundering

techniques. I am analysing a variety of substances and assessing their compatibility with diesel fuels as

potential markers using Gas Chromatography-Mass Spectrometry.

The Application of Desorption Electrospray Ionisation Hyphenated with Ion Mobility-Mass Spectrometry

for the Analysis of Oil and Oil Additives.

Caitlyn DaCosta, Colin Creaser (Department of Chemistry, University of Loughborough, UK)

Abstract

DESI-MS has been applied to the qualitative and quantitative determination of oils and oil additives directly

from a variety of surfaces with no prior sample preparation. Hyphenation of DESI-MS with ion mobility

techniques, such as triwave ion mobility (TWIMS) and a prototype high field asymmetric waveform ion

mobility device (FAIMS), is shown to enhance the selectivity and sensitivity of the technique for targeted

studies compared to DESI-MS alone. The use of DESI-FAIMS-MS for crude oil characterisation provides a

novel approach to improving separation of oil components.

Biography

I am a final year PhD student studying at Loughborough University under the supervision of Professor Colin

Creaser. The PhD is an EPSRC CASE studentship in association with Castrol Ltd focused on developing

desorption electrospray ionisation-mass spectrometry (DESI-MS) hyphenated with ion mobility for the

analysis of oils and oil additives directly from native surface materials. The developed techniques can enable

the rapid and direct analysis of automotive parts and oil transfer components with minimal sample

preparation. The work has centred around the design and construction of DESI ion sources that can be

hyphenated with tri-wave ion mobility (TWIMS) and high field asymmetric waveform ion mobility (FAIMS)

for the targeted analysis of oil additives in a complex oil matrix deposited on metal surfaces and for the

characterisation of crude oils.

Fatty Acid Methyl Esters (FAMEs) Issues and Hyphenated Mass Spectrometry Solutions

Waraporn Ratsameepakai, Julie Herniman and G John Langley (Chemistry, Faculty of Natural and

Environmental Sciences, University of Southampton, UK)

Abstract

FAME contamination in Aviation Turbine Fuel (AVTUR) can significantly impact the thermal stability and the

freezing point of AVTUR which can lead to engine operational problems. The existing ASTM reference

method for the determination of rapeseed methyl ester (RME, mainly C16 and C18 species) in AVTUR uses

GC-MS, but it cannot detect and quantify low carbon number FAMEs (C8-C14) from coconut oil, a feedstock

for FAME production in the Pacific region, and presently the international specifications limits FAME in

AVTUR to 5 mg/kg.[1]An analytical method that is able to detect all types of FAME in aviation fuel is required.

Herein Reversed phase high performance liquid chromatography - mass spectrometry (RP-HPLC-MS), ultra-

performance convergence chromatography – mass spectrometry (UPC2-MS), ultra-high performance

chromatography – mass spectrometry (UHPLC-MS) methods have been developed (5 mg/kg of FAME)

covering carbon ranges C8-C18.

The UPC2-MS and the UHPLC-MS methods are more than twenty times (UPC2-MS) and ~ ten times (UHPLC)

faster than the GC-MS reference method, provide linear dynamic range for the total FAME content with an

excellent linear correlation (R2 > 0.99) and are also more amenable to the analysis of lower chain length

methyl esters, e.g. coconut methyl ester. Further RP-HPLC-MS, UPC2-MS and UHPLC-MS methods have been

developed and utilised to follow the oxidation of FAMEs. The results showed up to four oxygen atoms

present in natural oxidation of RME.

References

[1] Joint Inspection Group. Fame update; Product Quality: Bulletin No. 61, Apr 2013.

Biography

Waraporn Ratsameepakai graduated with a master degree in Analytical Chemistry from the Prince of

Songkla University, Thailand in 2004 and began work as a scientist at the Scientific Equipment Centre within

the Prince of Songkla University, with work focussing on analytical instruments to analysis of the chemical

compounds of natural and artificial materials, and developing new analytical methods, to analysis of

biodiesel, particularly from palm and used frying oils. I was then awarded a scholarship from the Royal Thai

government to study for a PhD in chemistry.

Waraporn is now studying at University of Southampton under the supervision of Dr G John Langley; her

research is focused on the analysis of fuels and lubricants using mass spectrometry and separation science

techniques.

Solving Problems with Hyphenation

Tom Lynch (BP Technology Centre, Pangbourne, UK)

Abstract

The petroleum and petrochemical industry is highly regulated and the vast majority on analysis is carried out

using industry standard methods such as those published by ASTM, DIN or the Energy Institute. These

methods are also used to check for product quality excursions when field issues are encountered but in

many cases more sophisticated techniques are required. This presentation will describe approaches to

problem solving field issues using flexible hyphenated chromatographic and mass spectrometry systems. The

application of such systems using examples from a range of typical issues encountered in the petroleum and

related industries will be presented.

Biography

Tom Lynch is currently Team Leader of Investigational Analysis which provides a specialist forensic and

problem solving /method development capability for BP businesses. He is also a member of the BP Science

Council representing Analytical Science and leads a BP wide Analytical Science network.

Tom has published over 30 citable papers, 4 book chapters and has given over 60 presentations at

conferences. He has been a member of the International Organising and Scientific Committees for the HTC

conference series and is a member of the Editorial Advisory Board of LC-GC Europe and in 2003 he was

awarded the Silver Jubilee Medal by the Chromatographic Society. He is a past Vice President of the RSC

Analytical Division and a past Chairman of the RSC Separation Science Group.

GOLD SPONSOR PRESENTATIONS

Enhanced crude oil fingerprinting by GC x GC-TOF MS with soft electron ionisation

L. McGregor, S. Smith and N. Bukowski

Abstract

The enhanced separation offered by comprehensive two-dimensional gas chromatography with time-of-

flight mass spectrometry (GC x GC–TOF MS) has made the technique a popular choice for petrochemical

analyses.

Despite this enhanced separation, the identification of individual compounds in complex samples may

become complicated when similar mass spectral characteristics are evident across entire chemical classes.

Branched alkanes are a prime example, with weak molecular ions that further complicate the process.

Spectral similarity can be addressed by the use of soft ionisation to reduce the degree of ion fragmentation,

but this approach has been cumbersome to implement until now.

Select-eV ion-source technology aims to solve this problem through the ability to switch effortlessly between

hard and soft electron ionisation without loss in sensitivity. The novel ion source provides enhanced

molecular ions whilst retaining structurally-significant fragment ions, thus simplifying the identification of

isomeric compounds.

The enhanced sensitivity and selectivity stemming from the dramatic reduction in fragmentation at low

energies also greatly increases the number of compounds confidently identified, permitting robust statistical

comparisons which are essential for successful chemical fingerprinting.

High Resolution GC-TOF MS for Petrochemical Applications

Jürgen Wendt (LECO European LSCA Centre, Moenchengladbach, Germany)

Abstract

Petroleum is the most complex matrix in nature, constituted by many thousands of compounds, and

presents an analytical challenge. Different analytical techniques are used in the petroleum industry. Gas

chromatography coupled to high resolution time-of-flight mass spectrometry provides an extension of a

proven platform for petrochemical analysis. Concept, design and operation of a multi-reflecting TOF

instrument will be presented and explained. In addition, the utility of High Resolution GC-TOF MS for various

petrochemical applications will be discussed.

Developments in Orbitrap technology

Vincent Jespers (Thermo Scientific – Belgium)

Abstract

Can Orbitrap technology be applied to characterization of complex oil samples? What resolution do I need

for petrochemical analysis? Can I use UHPLC? Is a single analysis in positive and negative ionisation mode

possible? Is the dynamic range sufficient? These are all commonly asked questions by scientists and

researchers in the petrochemical industry. This presentation will introduce and describe the Orbitrap

technology and its application to petrochemical analysis. The presentation will demonstrate the ease of use,

mass accuracy and resolution of the Orbitrap technology for the robust analysis of petrochemical samples.