BARCHAN: Blob Alignment for Robust CHromatographic ANalysis (GCxGC)

In 1987, G. P. Barchan et al.  wrote a paper called: Gas chromatographic method of determining carbon monoxide and dioxide. But barkhan, or barchan, means more outside gas chromatography. It refers to sand dunes, with crescent shapes, modeled by the wind.

BARCHAN: crescent-shaped sand dunes

They inspired our image registration tool for comprehensive 2D chromatography peak alignment (GCxGC or GC2D). It was just published as BARCHAN: Blob Alignment for Robust CHromatographic ANalysis (GCxGC), Journal of Chromatography A, February 2017. For given 2D chromatogram areas of interest, a baseline removal (BEADS) is applied, a peak detection is performed, blobs are detected and registered with a mixed rigid/non-rigid transformation based on the Coherent Point Drift technique.

A pair of GCxGC chromatogram areas of interest.

BARCHAN registration, example.

The preprint is here. The HAL and the arxiv version. The abstract is next:

Abstract: (Comprehensive) Two dimensional gas chromatography (GCxGC) plays a central role into the elucidation of complex samples. The automation of the identification of peak areas is of prime interest to obtain a fast and repeatable analysis of chromatograms. To determine the concentration of compounds or pseudo-compounds, templates of blobs are defined and superimposed on a reference chromatogram. The templates then need to be modified when different chromatograms are recorded. In this study, we present a chromatogram and template alignment method based on peak registration called BARCHAN. Peaks are identified using a robust mathematical morphology tool. The alignment is performed by a probabilistic estimation of a rigid transformation along the first dimension, and a non-rigid transformation in the second dimension, taking into account noise, outliers and missing peaks in a fully automated way. Resulting aligned chromatograms and masks are presented on two datasets. The proposed algorithm proves to be fast and reliable. It significantly reduces the time to results for GCxGC analysis.

Highlights

• BARCHAN: 2D chromatogram and template alignment based on peak registration.

• The alignment is performed by probabilistic estimation with a Gaussian Mixture Model.

• It combines a rigid and a non-rigid transformation for complex samples analysis.

• The method accounts for noise, outliers and missing peaks in an automated way.

• BARCHAN significantly reduces the time to results for GC×GC analysis.

This work is a follow-up of preceding chromatography papers:

1. Chromatogram baseline estimation and denoising using sparsity (BEADS)
2. Comprehensive Two-Dimensional Gas Chromatography for Detailed Characterisation of Petroleum Products
3. Characterization of middle-distillates by comprehensive two-dimensional gas chromatography (GCxGC): a powerful alternative for performing various standard analysis of minewddle distillates
4. Comparison of conventional gas chromatography and comprehensive two-dimensional gas chromatography for the detailed analysis of petrochemical samples

A news-like description on IFP Energies nouvelles is provided:

(in French) at: Voyage au cœur des dunes pour des produits en quête d’identité, ou comment le traitement d’images accélère leur caractérisation
(in English) A journey to the heart of dunes for products in quest of identity, orhow image processing accelerates their characterization

Gas chromatography and 2D-gas chromatography for petroleum industry: The race for selectivity

Almost a follow-up to Signal Processing for Chemical Sensing: ICASSP 2013 Special session: the book Gas chromatography and 2D-gas chromatography for petroleum industry: The race for selectivity, edited by Fabrice Bertoncini, Marion Courtiade-Tholance, Didier Thiébaut (2013, éditions Technip) is out. Our contribution lies in Chapter 3: "Data processing applied to GCxGC. Applications to the petroleum industry.".

Detailed knowledge of petroleum products at molecular scale has always been essential to understand the mechanisms leading to their formation, to design thermodynamic and kinetic models employed in the refining processes and to predict their physical properties. In view of the complexity of petroleum products, very significant research efforts have been made over the past 15 years for improving relevant analytical techniques, especially in the field of Gas Chromatography in order to improve its separation power. The advent of comprehensive Two-dimensional Gas Chromatography (GC×GC) at the end of 1990's constitutes a true revolution allowing an unprecedented insight into very complex mixture at the molecular level.
This book aims at providing a complete review of the implementation of Gas Chromatography in the field of oil industry, with an important focus on GC×GC and related multidimensional systems. It is therefore organised into 8 chapters dealing with fundamental and experimental aspects as well as data processing challenges. Recent progress in the development of these chromatographic systems are discussed according to various applications: detailed molecular analysis of hydrocarbons, speciation of hetero-element, global properties calculation based on chromatographic data and simulated distillation. Specialists from IFP Energies nouvelles, CNRS and major companies leading important research in this field have contributed, reporting a synthesis of the knowledge acquired from research these last 15 years.
Thus, this book will be useful for anyone involved in the separation of oil and derivatives: the student starting a research project, the academic researcher and the refinery engineer willing to deepen their knowledge on advanced multidimensional Gas Chromatography, as well as molecular analysis of petroleum products.

 Contents: 1. Molecular analysis for petroleum products: challenges and future needs. 2. GCxGC: a disruptive technique. 3. Data processing applied to GCxGC. Applications to the petroleum industry. 4. Coupled systems with a CG or GCxGC dimension. 5. Detailed analysis of hydrocarbons. 6. Calculating properties from chromatographic data. 7. Speciation of heteroelements. 8. Simulated distillation. Index.

Related publications:  

Comprehensive Two-Dimensional Gas Chromatography for Detailed Characterisation of Petroleum Products ,Colombe Vendeuvre, R. Ruiz-Guerrero, Fabrice Bertoncini, Laurent Duval, Didier Thiébaut, Oil and Gas Science and Technology - Revue de l'IFP, Special issue on "Recent Advances in the Analysis of Catalysts and Petroleum Products", 2007, Vol. 62, n°01, p. 043-055

Comprehensive two-dimensional gas chromatography (GC xGC or GC2D) is a major advance for the detailed characterisation of petroleum products. This technique is based on two orthogonal dimensions of separation achieved by two chromatographic capillary columns of different chemistries and selectivities. High-frequency sampling between the two columns is achieved by a modulator, ensuring that the whole sample is transferred and analysed continuously in both separations. Thus, the peak capacity and the resoluting power dramatically increase. Besides, highly structured 2D chromatograms are obtained upon the volatility and the polarity of the solute to provide more accurate molecular identification of hydrocarbons. In this paper fundamental and practical considerations for implementation of GCxGC are reviewed. Selected applications obtained using a prototype of a GCxGC chromatograph developed in-house highlight the potential of the technique for molecular characterisation of middle distillates, sulphur speciation in diesel and analysis of effluents frompetrochemical processes

Characterization of middle-distillates by comprehensive two-dimensional gas chromatography (GCxGC): a powerful alternative for performing various standard analysis of middle distillates (pdf), Colombe Vendeuvre, Rosario Ruiz-Guerrero, Fabrice Bertoncini, Laurent Duval, Didier Thiébaut, Marie-Claire Hennion, Journal of Chromatography A, 1086 (2005) p. 21-28

The detailed characterisation of middle distillates is essential for a better understanding of reactions involved in refining process. Owing to higher resolution power and enhanced sensitivity, comprehensive two-dimensional gas chromatography (GCxGC) is a powerful tool for improving characterisation of petroleum samples. The aim of this paper is to compare GCxGC and various ASTM methods – gas chromatography (GC), liquid chromatography (LC) and mass spectrometry (MS) – for group type separation and detailed hydrocarbon analysis. Best features of GCxGC are demonstrated and compared to these techniques in terms of cost, time consumption and accuracy. In particular, a new approach of simulated distillation (SimDis-GCxGC) is proposed: compared to the standard method ASTM D2887 it gives unequal information for better understanding of conversion process.

Comparison of conventional gas chromatography and comprehensive two-dimensional gas chromatography for the detailed analysis of petrochemical samples (pdf), Colombe Vendeuvre, Fabrice Bertoncini, Laurent Duval, Jean-Luc Duplan, Didier Thiébaut, Marie-Claire Hennion, Journal of Chromatography A, 1056 (2004) p. 155-162

Comprehensive two-dimensional gas chromatography (GCxGC) has been investigated for the characterization of high valuable petrochemical samples from dehydrogenation of n-paraffins, Fischer–Tropsch and oligomerization processes. GCxGC separations, performed using a dual-jets CO2 modulator, were optimized using a test mixture representative of the hydrocarbons found in petrochemicals. For complex samples, a comparison of GCxGC qualitative and quantitative results with conventional gas chromatography (1D-GC) has demonstrated an improved resolution power of major importance for the processes: the group type separation has permitted the detection of aromatic compounds in the products from dehydrogenation of n-paraffins and from oligomerization, and the separation of alcohols from other hydrocarbons in Fischer–Tropsch products.

Call for papers: Advances in signal and image processing for physico-chemical analysis

(CfP: Deadline extension) Looking for new frontiers in signal and image processing applications in physico-chemical analysis? Have compressive sensing results for mass spectrometry? Got improvements on the Savitsky-Golay filter? Consider the following call for contributions.

 Call for papers: Dossier, Special issue on Advances in signal and image processing for physico-chemical analysis (pdf)

Deadlines : Final manuscript: February 17th, 2012

Oil & Gas Science and Technology - Revue d'IFP Energies Nouvelles (online journal) 

WikiCfP: OGST-SIP-PCA

With the advent of more affordable, higher resolution or innovative data acquisition techniques (for instance hyphenated instrumentation such as two-dimensional chromatography), the need for advanced signal and image processing tools has grown in physico-chemical analysis, together with the quantity and complexity of acquired measurements. Either with mono- (signals) or two-dimensional (from hyphenated techniques to standard images) data, processing generally aims at improving quality and at providing more precise quantitative assessment of measurements of materials and products, to yield insight or access to information, chemical properties, reactive dynamics or textural properties, to name a few (for instance). Although chemometrics embrace from experimental design to calibration, more interplay between physico-chemical analysis and generic signal and image processing is believed to strengthen the two disciplines. Indeed, although they strongly differ in background and vocabulary, both specialities share similar values of best practice in carrying out identifications and comprehensive characterizations, albethey of samples or of numerical data.
The present call for papers aims at gathering contributions on recent progresses performed and emerging trends concerning (but not limited) to:

• 1D and 2D acquisition, sparse sampling (compressive sensing), modulation/demodulation, compression, background/baseline/trend estimation, enhancement, integration, smoothing and filtering, denoising, differentiation, detection, deconvolution and source separation, resolution improvement, peak or curve fitting and matching, clustering, segmentation, multiresolution analysis (wavelets), mathematical morphology, calibration, multivariate curve resolution, property prediction, regression, data mining, tomography, visualization,

pertaining to the improvement of physico-chemical analysis techniques, including (not exclusively):

• (high-performance) gas, liquid or ion chromatography; gel electrophoresis; diode array detector; Ultraviolet (UV), visible, Infrared (NIR, FIR), Raman or Nuclear Magnetic Resonance (NMR) spectroscopy, X-ray diffraction (XRD), X-Ray Absorption (EXAFS, XANES), mass spectrometry; photoacoustic spectroscopy (PAS); porosimetry; hyphenated techniques (GCxGC); electron microscopy (SEM, TEM),

in the following proposed domains (not exclusively):

• catalysis, chemical engineering, oil and gas production, refining processes, petrochemicals, and other sources of energy, in particular alternative energies with a view to sustainable development.

Provisional deadlines:

• Statement of intent: January 31st, 2012
• Submission of final manuscript: February 17th, 2012
• Publication: 2nd semester 2012 

Refering links:
Thierry Gallouët Igor Carron at Nuit Blanche in Around the blogs in 80 hours, Harris Georgiou, GdR ISIS

More details:
http://tinyurl.com/ogst-signal-chemical-analysis
http://www.laurent-duval.eu/lcd-cfp-ogst-2012-call-for-papers-signal-image-processing-physico-chemical-analysis.html