Near-Infrared Spectroscopy Analysis of Heavy Fuel Oils Using a New Diffusing Support.

The characterization of heavy fuel oils (HFOs), used as fuel for boats, requires the analysis of various properties that are essential for engine optimization and pollution control. For some time, near-infrared (NIR) spectroscopy combined with chemometric treatment of the spectra was used for on-line analysis. This preliminary study included 61 heavy fuels from Europe, America, and Asia with different specifications according to their geographical origin; their refining process; and their physicochemical properties, including density, flash point, viscosity, and sulfur content. We have developed a new method for sampling heavy fuels on a fiberglass cell support. This support offers the advantages of speed, easy implementation, repeatable results, and freedom from problems associated with tank cleaning. Two sample presentations, an integrating sphere and an optical fiber, were used to collect the NIR spectra. A theoretical study of the choice of the value of resolution, scan number, and spectral region was conducted. The best conditions were chosen as a function of the quality of quantitative analysis results on viscosity, sulfur content, flash point, and density. The two collecting methods were compared on the same criteria.

Simulated aging of lubricant oils by chemometric treatment of infrared spectra: potential antioxidant properties of sulfur structures.

Lubricant oils are complex mixtures of base oils and additives. The evolution of their performance over time strongly depends on its resistance to thermal oxidation. Sulfur compounds revealed interesting antioxidant properties. This study presents a method to evaluate the lubricant oil oxidation. Two samples, a synthetic and a paraffinic base oils, were tested pure and supplemented with seven different sulfur compounds. An aging cell adapted to a Fourier Transform InfraRed (FT-IR) spectrometer allows the continuous and direct analysis of the oxidative aging of base oils. Two approaches were applied to study the oxidation/anti-oxidation phenomena. The first one leads to define a new oxidative spectroscopic index based on a reduced spectral range where the modifications have been noticed (from 3050 to 2750 cm(-1)). The second method is based on chemometric treatments of whole spectra (from 4000 to 400 cm(-1)) to extract underlying information. A SIMPLe-to-use Interactive Self Modeling Analysis (SIMPLISMA) method has been used to identify more precisely the chemical species produced or degraded during the thermal treatment and to follow their evolution. Pure spectra of different species present in oil were obtained without prior information of their existence. The interest of this tool is to supply relative quantitative information reflecting evolution of the relative abundance of the different products over thermal aging. Results obtained by these two ways have been compared to estimate their concordance.

Automated principal component-based orthogonal signal correction applied to fused near infrared-mid-infrared spectra of French olive oils.

An approach for automating the determination of the number of components in orthogonal signal correction (OSC) has been devised. In addition, a novel principal component OSC (PC-OSC) is reported that builds softer models for removing background from signals and is much faster than the partial least-squares (PLS) based OSC algorithm. These signal correction methods were evaluated by classifying fused near- and mid-infrared spectra of French olive oils by geographic origin. Two classification methods, partial least-squares-discriminant analysis (PLS-DA) and a fuzzy rule-building expert system (FuRES), were used to evaluate the signal correction of the fused vibrational spectra from the olive oils. The number of components was determined by using bootstrap Latin partitions (BLPs) in the signal correction routine and maximizing the average projected difference resolution (PDR). The same approach was used to select the number of latent variables in the PLS-DA evaluation and perfect classification was obtained. Biased PLS-DA models were also evaluated that optimized the number of latent variables to yield the minimum prediction error. Fuzzy or soft classification systems benefit from background removal. The FuRES prediction results did not differ significantly from the results that were obtained using either the unbiased or biased PLS-DA methods, but was an order of magnitude faster in the evaluations when a sufficient number of PC-OSC components were selected. The importance of bootstrapping was demonstrated for the automated OSC and PC-OSC methods. In addition, the PLS-DA algorithms were also automated using BLPs and proved effective.

A rheological method to evaluate the physical stability of highly viscous pharmaceutical oil-in-water emulsions.

PURPOSE: The aim of this study was to develop a rheological method to evaluate the stability of highly viscous pharmaceutical emulsions. Thereby, the time devoted to the storage tests could be reduced and manufacturers could save time in optimizing their formulations and manufacturing techniques for topical pharmaceutical forms. The influence of the type of oil and the type of emulsifier on the microstructure of the emulsions was also studied. MATERIALS AND METHODS: The samples were stored at 25 and at 50 degrees C for 6 months and analysed every month using rheological as well as microscopic techniques. The size and the organization of the droplets within the emulsion were determined by freeze-fracture electron microscopy and optical contrast phase microscopy. RESULTS: A decrease in the rheological parameters was observed for the OC emulsions ("Tween/Span" emulsions made with olive oil) and the "Montanov" emulsions. The rheological measurements showed that the structure of the OC emulsions and that of the emulsions made with the Montanov 82 emulsifier become more brittle when submitted to a shear force. The micrographs obtained by freeze-fracture electron microscopy showed that for OC only the oil droplets arrange in a network structure. Storage tests at 50 degrees C confirmed the rheological assumptions on the stability of emulsions. CONCLUSION: The study of the effect of shearing on the emulsions allowed quick discrimination between the emulsions according to their stabilities. The rheological tool gave information on the structure of the emulsions and on the aging process.

Prediction of source rock origin by chemometric analysis of fourier transform infrared-attenuated total reflectance spectra of oil petroleum: evaluation of aliphatic and aromatic fractions by self-modeling mixture analysis.

This study describes a new methodology for the interpretation of Fourier transform infrared (FT-IR) attenuated total reflectance (ATR) spectra of Algerian, Brazilian, and Venezuelan crude oils. It is based on a comparative study between a chemometric treatment and the classical one, which refers to indices calculation. In fact, the combined use of FT-IR indices and principal component analysis (PCA) has led to the classification of the studied samples in terms of geographic distribution. Quantitative analysis has been successfully realized by the supervised method partial least squares (PLS), which has permitted the prediction of the locations of oils. We have also applied another mathematical processing method, simple-to-use interactive self-modeling mixture analysis (SIMPLISMA), to evaluate the aromatic and aliphatic composition of the oils by extracting pure spectra representative of the different fractions.

Origin of French virgin olive oil registered designation of origins predicted by chemometric analysis of synchronous excitation-emission fluorescence spectra.

The authentication of virgin olive oil samples requires usually the use of sophisticated and very expensive analytical techniques, so there is a need for fast and inexpensive analytical techniques for use in a quality control methodology. Virgin olive oils present an intense fluorescence spectra. Synchronous excitation-emission fluorescence spectroscopy (SEEFS) was assessed for origin determination of virgin olive oil samples from five French registered designation of origins (RDOs) (Nyons, Vallée des Baux, Aix-en-Provence, Haute-Provence, and Nice). The spectra present bands between 600 and 700 nm in emission due to chlorophylls a and b and pheophytins a and b. The bands between 275 and 400 nm in emission were attributed to alpha-, beta-, and gamma-tocopherols and to phenolic compounds, which characterize the virgin olive oils compared to other edible oils. The chemometric treatment (PLS1) of synchronous excitation-emission fluorescence spectra allows one to determine the origin of the oils from five French RDOs (Baux, Aix, Haute-Provence, Nice, and Nyons). Results were quite satisfactory, despite the similarity between two denominations of origin (Baux and Aix) that are composed by some common cultivars (Aglandau and Salonenque). The interpretation of the regression coefficients shows that RDOs are correlated to chlorophylls, pheophytins, tocopherols, and phenols compounds, which are different for each origin. SEEFS is part of a global analytic methodology that associates spectroscopic and chromatographic techniques. This approach can be used for traceability and vindicates the RDOs.