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
Registration Fee: All Presentations, Exhibition, and Lunch
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Please register here
https://events.rsc.org/rsc/529/register
http://www.rsc.org/events/detail/11943/recent-approaches-to-meet-the-petrochemical-challenge
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 twodimensional 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), ultraperformance 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-offlight 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.