An original deconvolution approach for oil production allocation based on geochemical fingerprinting

We tackle oil commingling scenarios and develop an original deconvolution approach for geochemical production allocation. This yields robust assessment of the proportions of oils forming a mixture originating from commingling oils associated with diverse reservoirs or, wells. Our study starts from considering that production allocation performed by means of geochemical fingerprinting is relevant in the context of modern and sustainable use of georesources, with the added benefit of favoring shared facilities and production equipment. A geochemical production allocation workflow is typically structured according to two steps: (i) determination of the chromatograms associated with the mixture (and eventually with each of the End Members, EMs, constituting the fluids in the mixture), and (ii) the use of a deconvolution algorithm to estimate the mass fraction of each EM. Concerning the latter step, we introduce an original approach and the ensuing deconvolution algorithm (hereafter termed PGM) that does not require additional laboratory efforts in comparison with traditional approaches. We also present extensions of widely used deconvolution algorithms, which we frame in a (stochastic) Monte Carlo context to improve their robustness and reliability. The new PGM approach is assessed jointly with a suite of typically used approaches and algorithms against new laboratory-based commingling scenarios. The latter are based on the design and introduction of a novel and low-cost experimental method. The results of the study (i) constitute a unique and rigorous comparison of the traditionally employed production allocation deconvolution algorithms, (ii) document the critical importance of the number of features of the chromatograms used during a quantitative deconvolution, and (iii) suggest that our new PGM approach is very robust and accurate compared to existing approaches

Application of Liquid Chromatography in Food Analysis

Food products are very complex mixtures consisting of naturally occurring compounds and other substances, generally originating from technological processes, agrochemical treatments, or packaging materials. However, food is no longer just a biological necessity for survival. Society demands healthy and safe food, but it is also increasingly interested in other quality attributes more related to the origin of the food, the agricultural production processes used, the presence or not of functional compounds, etc. Improved methods for the determination of authenticity, standardization, and efficacy of nutritional properties in natural food products are required to guarantee their quality and for the growth and regulation of the market. Nowadays, liquid chromatography with ultraviolet detection, or coupled to mass spectrometry and high-resolution mass spectrometry, are among the most powerful techniques to address food safety issues and to guarantee food authenticity in order to prevent fraud. The aim of this book is to gather review articles and original research papers focused on the development of analytical techniques based on liquid chromatography for the analysis of food. This book is comprised of six valuable scientific contributions, including five original research manuscripts and one review article, dealing with the employment of liquid chromatography techniques for the characterization and analysis of feed and food, including fruits, extra virgin olive oils, confectionery oils, sparkling wines and soybeans

Advances in Chemical Analysis Procedures (Part I)

The availability (and the development) of innovative approaches to quantitative analyses and the data processing are often mandatory to deeply characterize a sample and to correctly highlight the analytical target. These objectives are carried out either by simply improving a single aspect of the analytical protocol or by developing a synergy of steps (from extraction to instrumental configuration to chemometric approaches) to obtain the maximum analytical information sought. Examples are innovative extraction protocols (also following the recent guidelines on green analytical chemistry) or new materials for the selective extraction of target compounds, multi-analytes screening methods, and "untargeted" approaches for food applications. In this text, the various articles are attributable to these elements, in particular, we start with a multi-analyte method for the determination of 10 different cannabinoids from Cannabis sativa L. by means of conventional techniques (Mandrioli and coworkers), to then see the application of techniques hyphenated "ultra-fast" by UPLC-MS for the authentication of food products (Xue and coworkers). The work of Song and coworkers on these applications in food products is also interesting, as it highlights how the collection process (and the timing of this passage) can affect the chemical profile and, consequently, the biological activity of Panax ginseng. Mocan and coworkers, applying an innovative extraction technique based on microwaves and applying well-known, robust, and easy-to-use instrumentation, have demonstrated how it is possible to discriminate between various species of Galium and how the chemical profiles obtained can support the biological activities observed. Similarly, but with the aim of developing new sample pretreatment procedures, Maggira and collaborators have developed graphene oxide-based materials for the selective extraction of sulfonamides in milk. Shen and coworkers apply a different type of approach, the "untargeted" one, for the geographical characterization of the Gentian Rigescens for which they combine chemometric techniques for the processing of raw chemical profile data. Wang and coworkers report a multiclass screening of drugs with high-resolution mass spectrometry through which they manage to obtain a high-scale, fast screening method for pesticides in fishery drugs based on ultrahigh-performance liquid chromatography tandem quadrupole-orbitrap high-resolution mass spectrometer

Use Capacitance-Resistance Model to Characterize Water Flooding in A Tight Oil Reservoir

Gaither Draw Unit is a heterogeneous and tight formation with an average permeability of 0.1 mD. After more than 1.7 MMSTB water has been injected, there was no clear signal indicating the injected water from any producer. However, knowing the distribution of injected water is critical for future well planning and quantifying the efficiency of injection. The objective of this study is to show how the Capacitance-Resistance Model (CRM) was used to study this field and how the results were validated using traditional reservoir simulation. The CRM model quantitatively describes the connectivity and the degree of fluid storage between injectors and producers only from injection and production rate data. On the basis of material balance, signals from injectors to producers can be represented in the CRM model. The connectivity between each injector/producer pair of a selected portion of the field is estimated by using a constrained nonlinear multivariable optimization technique. The fitting results of the connectivity and the time constant through the CRM analysis indicate the regional permeability heterogeneity, which is consistent with Computer Modelling Group, Ltd. (CMG) full field modelling. The time constants conform to the low permeability of a tight formation. The history matched CMG full field model and results from the CRM analysis both present similar pressure distributions. It indicates that the majority of the injected water mainly saturates the regions surrounding the injectors, and the low transmissibility prevents pressure dissipation

Development of High Resolution Mass Spectrometric Methods for the investigation of food authenticity

Η αυθεντικότητα των τροφίμων αποτελεί ένα ιδαίτερα σημαντικό γεγονός τα τελευταία χρόνια, λόγω των πολλών περιστατικών νοθείας τροφίμων και διακίνησης προϊόντων κατώτερης ποιότητας με παραπλανητικές ετικέτες. Η εξασφάλιση της αυθεντικότητας του ελαιολάδου δημιουργεί μεγάλη ανησυχία λόγω της οργανοληπτικής, θρεπτικής και οικονομικής του σημασίας. Ο κύριος στόχος αυτής της διατριβής είναι η ανάπτυξη αναλυτικών μεθόδων υγροχρωματογραφίας φασματομετρίας μάζας υψηλής διακριτικής ικανότητας (LC-HRMS) που θα συμπεριλαμβάνουν στρατηγικές στοχευμένης, «ύποπτης» και «μη στοχευμένης σάρωσης», σε συνδυασμό με προηγμένα χημειομετρικά εργαλεία, για την εύρεση του αποτυπώματος του ελαιολάδου. Aρχικά, αναφέρονται οι βιολογικές δράσεις των ελάσσονων συστατικών του ελαιολάδου, των φαινολικών ενώσεων, και οι επιδράσεις διαφόρων παραγόντων στο φαινολικό προφίλ. Παρουσιάζονται όλες οι σύγχρονες και αναλυτικές μέθοδοι που συνδυάζουν την επιστήμη των τροφίμων με τεχνικές μεταβολομικής, με έμφαση στις μεθόδους HR-MS. Το πειραματικό μέρος της διατριβής αποτελείται από τρία τμήματα: (1) Μελέτες αυθεντικότητας ελαιολάδου με LC-QTOF-MS σε συνδυασμό με στοχευμένη και μη στοχευμένη σάρωση και χημειομετρία για την αναγνώριση δεικτών που κατατάσσουν το ελαιόλαδο ως ελαττωματικό ή έξτρα παρθένο. (Κεφάλαιο 3), (2) Διερεύνηση του βιολογικού και συμβατικού τύπου παραγωγής των έξτρα παρθένων ελαιολάδων με LC-QTOF-MS σε συνδυασμό με στοχευμένη και «ύποπτη» σάρωση, προτείνοντας μια νέα μέθοδο ημι-ποσοτικοποίησης (Κεφάλαιο 4), και (3) Ταξινόμηση έξι ελληνικών ποικιλιών ελαιoλάδου με LC-QTOF-MS μη στοχευμένη στοχευμένη σάρωση και χημειομετρία, για την αναγνώριση δεικτών με προκαθορισμένα όρια συγκέντρωσης, που εγγυώνται την ποικιλιακή και γεωγραφική προέλευση (Κεφάλαιο 5). Πιστεύουμε ότι οι παραπάνω μελέτες έχουν σημειώσει μεγάλη πρόοδο στον τομέα της γνησιότητας των τροφίμων με την ανάπτυξη αναλυτικών μεθόδων HR-MS και μέσω της εισαγωγής μιας νέας ολοκληρωμένης ροής εργασιών που περιλαμβάνει στρατηγικές στοχευμένης, «ύποπτης» και μη στοχευμένης σάρωσης HRMS, σε συνδυασμό με, ολοκληρωμένα εργαλεία εξόρυξης, επεξεργασίας δεδομένων και προγνωστικά μοντέλα.Food authenticity has become increasingly important in recent years due to food fraud incidents and the handling of low quality products with misleading labels. The guarantee of the authenticity of olive oil arises great public concern because of its sensory, nutritional and economic importance. The main objective of this thesis is to develop integrated LC-HRMS workflows, including target, suspect and non-target screening strategies, coupled with advanced chemometric tools, for olive oil fingerprinting. First, the biological activities of some minor constituents in olive oil, phenolic compounds, are reported and their occurrence and wide-scope properties in olive matrices, as well as effects of various factors on olive oil phenolic profile, are discussed. The present state of the art for their determination in foodomics science is presented, focusing on target and non-target screening HR-MS workflows coupled to chemometrics. The experimental section of the thesis consists of three sections: (1) Olive oil authenticity studies by target and non-target LC-QTOF-MS combined with advanced chemometrics, for identifying markers that classify olive oil to defective and EVOOs (Chapter 3), (2) Investigating the organic and conventional production type of EVOOs with target and suspect screening by LC-QTOF-MS, a novel semi-quantification method using chemical similarity and advanced chemometris; in order to identify a marker with a concentration threshold, by ACO/RF, that can be used to discriminate organic and conventional EVOOs (Chapter 4), and (3) Classification of Greek olive oil varieties with non-target UHPLC-QTOF-MS and advanced chemometrics; for the investigation of the fingerprints of six greek olive oil varieties and the identification of markers, with post-defined concentration thresholds, that guarantee the varietal and geographical origin (Chapter 5). We believe that these studies have made great progress in the food authenticity field via the introduction of novel integrated HRMS screening workflows which are followed by advanced data processing, comprehensive data mining and predictive modelling tools

Practical Applications of NMR to Solve Real-World Problems

Nuclear magnetic resonance spectroscopy (NMR) has developed from primarily a method of academic study into a recognized technology that has advanced measurement capabilities within many different industrial sectors. These sectors include areas such as national security, energy, forensics, life sciences, pharmaceuticals, etc. Despite this diversity, these applications have many shared technical challenges and regulatory burdens, yet interdisciplinary cross-talk is often limited. To facilitate the sharing of knowledge, this Special Issue presents technical articles from four different areas, including the oil industry, nanostructured systems and materials, metabolomics, and biologics. These areas use NMR or magnetic resonance imaging (MRI) technologies that range from low-field relaxometry to magnetic fields as high as 700 MHz. Each article represents a practical application of NMR. A few articles are focused on basic research concepts, which will likely have the cross-cutting effect of advancing multiple disciplinary areas