Synchronous fluorescence and excitation emission characteristics of transformer oil ageing

This paper describes the evaluation of synchronous fluorescence spectroscopy (SFS) and excitation emission matrix fluorescence (EEMF) spectroscopy as means of monitoring transformer oil degradation. When accelerated thermal ageing method is used, the onset of degradation of transformer oil on 17th day and transformer oil with polypropylene and cellulosic paper on 23rd and 27th days is sensitively reflected in the SFS and EEMF fluorescence spectral characteristics.     

A multidimensional gas chromatography method for the analysis of hydrogen sulfide in crude oil and crude oil headspace

Two‐dimensional heart‐cutting gas chromatography is used to analyze dissolved hydrogen sulfide in crude samples. Liquid samples are separated first on an HP‐PONA column, and the light sulfur gases are heart‐cut to a GasPro column, where hydrogen sulfide is separated from other light sulfur gases and detected with a sulfur chemiluminescence detector. Heart‐cutting is accomplished with the use of a Deans switch. Backflushing the columns after hydrogen sulfide detection eliminates any problems caused by high‐boiling hydrocarbons in the samples. Dissolved hydrogen sulfide is quantified in 14 crude oil samples, and the results are shown in this work. The method is also applicable to the analysis of headspace hydrogen sulfide over crude oil samples. Gas hydrogen sulfide measurements are compared to liquid hydrogen sulfide measurements for the same sample set. The chromatographic system design is discussed, and chromatograms of representative gas and liquid measurements are shown.     

Classification of edible and lampante virgin olive oil based on synchronous fluorescence and total luminescence spectroscopy

Total luminescence and synchronous fluorescence spectroscopies were tested as regards their ability to differentiate edible from lampante virgin olive oils. Total luminescence spectra were recorded by measuring the emission spectra in the range 350-720 nm at excitation wavelengths from 320 to 535 nm. The synchronous fluorescence spectra of 41 edible and 32 lampante virgin olive oils were acquired by synchronous scanning the excitation and emission monochromator maintained at an offset value of 80 nm. Classification of virgin olive oils based on their synchronous fluorescence spectra was performed by hierarchical cluster analysis and principal component analysis using the spectral range of 429-545 nm. Principal component analysis provided better discrimination between the two classes, without any classification error, while hierarchical cluster analysis allowed 97.3% correct classification. These results indicate the capability of fluorescence techniques to differentiate virgin olive oils according to their quality.     

Mass-spectrometric analysis of complex volatile and nonvolatile crude oil components: a challenge

Crude oil analysis has long been an inspiration for the development of analytical techniques. Especially mass spectrometry has flourished as a result of the challenge these extremely complex problems offer. Here an overview of different analytical methods is presented that shows different ways to analyze volatile and nonvolatile crude oil components. Focus has been placed on the use of mass spectrometry and especially the new developments that have been introduced using the emerging technique of Fourier transform ion cyclotron resonance mass spectrometry. These studies are examples of how far the development of analytical methods has come for the task of studying such complex problems.     

Synchronous fluorescence spectroscopy for quantitative determination of virgin olive oil adulteration with sunflower oil

Adulteration of extra virgin olive oil with sunflower oil is a major issue for the olive oil industry. In this paper, the potential of total synchronous fluorescence (TSyF) spectra to differentiate virgin olive oil from sunflower oil and synchronous fluorescence (SyF) spectra combined with multivariate analysis to assess the adulteration of virgin olive oil are demonstrated. TSyF spectra were acquired by varying the excitation wavelength in the region 270–720 nm and the wavelength interval (Δλ) in the region from 20 to 120 nm. TSyF contour plots for sunflower, in contrast to virgin olive oil, show a fluorescence region in the excitation wavelength range 325–385 nm. Fifteen different virgin olive oil samples were adulterated with sunflower oil at varying levels (0.5–95%) resulting in one hundred and thirty six mixtures. The partial least-squares regression model was used for quantification of the adulteration using wavelength intervals of 20 and 80 nm. This technique is useful for detection of sunflower oil in virgin olive oil at levels down to 3.4% (w/v) in just two and a half minutes using an 80-nm wavelength interval.     

Liquid chromatography fractionation with gas chromatography/mass spectrometry and preparative gas chromatography-nuclear magnetic resonance analysis of selected nonylphenol polyethoxylates

Commercial nonylphenol polyethoxylates, designated as NPnEOs, where n is the number of ethoxy groups, comprise a range of ethoxylate groups. According to the starting material nonylphenol, they may also be composed of a complex mix of isomeric nonyl substituents. In order to study more fully the heterogeneity arising from both the ethoxylate and nonyl groups, a mixture of NPnEOs is first fractionated by normal phase liquid chromatography (NPLC) into separate fractions comprising individual ethoxymers, n. Preparative collection of each early elution ethoxymer fraction allows further separation of different isomeric nonyl group components by using analytical gas chromatography/mass spectrometry (GC/MS). The nonyl isomers are not resolved in the NPLC method. The distribution of the isomeric nonyl side chain of different ethoxymers bears close resemblance with each other, and also with the original nonylphenol starting material, although separation efficiency of the nonyl isomers for each ethoxymer decreases with increasing ethoxymer number. Mass spectrometry of the separated isomers display close similarity for presumed equivalent isomers in each fraction, based on elution order of the nonyl isomers. This suggests that each corresponding peak has the same isomer structure. Mass spectra are interpreted based on branching within the nonyl side chain. Preparative GC coupled with MS and nuclear magnetic resonance spectroscopy elucidated the molecular structure of one of the resolved isomers as 4-(1,3-dimethyl-1-propyl-butyl)-phenol diethoxylate.     

Determination of petroleum sulfonates in crude oil by column-switching anion-exchange chromatography

A column-switching anion-exchange chromatography method was described for the separation and determination of petroleum monosulfonates （PMS） and petroleum disulfonates （PDS） in crude oil that was simply diluted with the dichloromethane/methanol （60/40）. The high performance liquid chromatography （HPLC） system consisted of a clean-up column and an analytical column, which were connected with two six-port switching valves. Detection of petroleum sulfonates was available and repeatable. This method has been successfully applied to determine PMS and PDS in crude oil samples from Shengli oil field.     

Mercury speciation in thawed out and refrozen fish samples by gas chromatography coupled to inductively coupled plasma mass spectrometry and atomic fluorescence spectroscopy

Different sub-sampling procedures were applied for the determination of mercury species (as total mercury Hg, methylmercury MeHg⁺ and inorganic mercury Hg²⁺) in frozen fish meat. Analyses were carried out by two different techniques. After the sample material was pre-treated by microwave digestion, atomic fluorescence spectroscopy (AFS) was used for the determination of total Hg. Speciation analysis was performed according to the following procedure: dissolution of sample material in tetramethylammonium hydroxide (TMAH), derivatisation with sodium tetraethylborate (NaBEt₄), extraction into isooctane and measurement with gas chromatography inductively coupled plasma mass spectrometry (GC-ICPMS) for the identification and quantification of methylmercury (MeHg⁺) and inorganic mercury (Hg²⁺). The concentration range of total Hg measured in the shark fillets is between 0.9 and 3.6 g g^–1 thawed out shark fillet. Speciation analysis leads to 94% Hg present as MeHg⁺. Homogeneity, storage conditions and stability of analytical species and sample materials have great influence on analytical results. Sub-sampling of half-frozen/partly thawed out fish and analysis lead to significantly different concentrations, which are on average a factor of two lower.     

Comparison of gas and liquid chromatography coupled to mass spectrometry for the residue analysis of pesticides in organges

Summary Liquid chromatography-mass spectrometry (LC-MS) with atmospheric pressure chemical ionization (APCI), and gas chromatography-mass spectrometry (GC-MS) with electron impact ionization (EI), are compared for the determination of eight pesticides in oranges. Seven of the selected pesticides, chlorpyriphos, chlorpyriphos-methyl, imazalil, α and β-endosulfan, endosulfan sulphate and dicofol, are commonly determined by GC whereas one, thiabendazole, can only be directly determined by LC. Primary ions [M-H]⁻ or [M-Cl+O]⁻ are obtained using LC-APCI-MS in negative ionization (NI) mode. In contrast, a high degree of fragmentation is reported with GC-MS. Both techniques were applied to oranges, which had been previously extracted with ethyl acetate and anhydrous sodium sulphate. The data indicate equivalent detection limits that range from 0.01 to 0.1 mgkg⁻¹ and similar degree of specificity. Mean recoveries ranged from 82% for α-endosulfant to 96% for imazalil, with relative standard deviation ranging from 7 to 17%.     

Capillary gas chromatography/mass spectrometry of aza-arenes isolated from crude coal tar

Summary The basic fraction of crude coal tar was isolated in a two-step partition process. Its constituents, mostly azaarenes up to four-ring structures, were resolved on a Superox-coated glass capillary column and tentatively identified by combined gas chromatography/mass spectrometry.     

Detection in urine of efaproxiral (RSR13), a potential doping agent, by a routine screening procedure based on methylation followed by gas chromatography/mass spectrometry

Efaproxiral (also known as RSR13) is a synthetic allosteric modifier of hemoglobin. The ability to increase maximal muscle oxygen uptake makes RSR13 a potential performance-enhancing agent for athletes and, therefore, a new agent to be taken into account by the antidoping control laboratories. In this work, a new method for the detection of efaproxiral in urine by gas chromatography/mass spectrometry is described.     

Distribution of weight,density, and molecular weight in crude oil derived from computerized capillary GC analysis

Chromatographic separation of crude oil components has been performed on a 50 m Chrompack Sil 5 fused silica capillary column, temperature programmed from 10 to 300°C. Approximately 70 peaks eluting before n-nonane (n-C₉) and all normal paraffins to n-C₁₉ were identified by a retention time table. Peak areas were converted to weight % using 1-heptene as internal standard and relative response factors. Components were divided into boiling range groups from n-C₆ to n-C₁₉. Paraffinic, naphthenic, and aromatic distributions were obtained for the boiling point fractions up to n-C₉. Group average densities and molecular weights were calculated from pure component properties up to n-C₉. Knowing the density and molecular weight as functions of boiling range group to n-C₉, these functions can be extrapolated to n-C₁₉, based on data and correlations from more than 20 distillations of paraffinic North Sea oils adn condensates. The densities and molecular weights of the C₁₀+ and the C₂₀+ residues were calculated to satisfy a balance of weight, volume, and number of moles for the whole sample. Measurements on the residues were used to cross-evaluate the GC method against distillation. The difference in weight was estimated to be less than ± 0.5% in absolute terms for the C₁₀+ residue. The corresponding figure for C₂₀+ was ± 2%. Relatively, calculated densities are within ± 1%, molecular weights within ± 2% compared to direct measurements. Calculations were performed by a BASIC program in a GC interfaced computer.     

Direct analysis of alkylnaphthalenes in crude oils by two-dimensional capillary gas chromatography

Summary Diaromatics are geochemically significant constituents of crude oils. Their determination is usually achieved by elaborate prefractionation methods, such as medium pressure liquid chromatography and HPLC, prior to capillary gas chromatography. The present contribution describes the quantitative analysis of methylnaphthalenes, ethylnaphthalenes, and dimethylnaphthalenes in selected crude oils by two-dimensional capillary GC. Since the method does not comprise any work-up procedure the determination of geochemical parameters (alkylnaphthalene concentration ratios) is performed on the original, untreated crude oil samples. Accordingly, the analytical results reflect the original composition. The influence by evaporational losses in the laboratory is minimized.     

Estimation of crude oil grade using time-resolved fluorescence spectra

Time-resolved fluorescence (TRF) spectra of six crude oils from the eastern province of Saudi Arabia were excited using a pulsed laser radiation at 250 nm and measured at specific time gates (TG) within the leading and trailing edges of the laser temporal pulse. The spectra showed the presence of a shoulder near 380 nm that systematically decreased in intensity from high-grade to low-grade crudes, and also from earlier to later TGs. The intensities of these shoulders are shown to be useful in estimating the grades of crude oils, particularly when the TRF spectra are measured at TGs within the leading edge of the laser temporal pulse. Contour diagrams depicting the shapes of the TRF spectra as function of TG (within the leading and trailing edges) are also presented to serve as true fingerprints of the crudes.     

Analysis of Alaskan crude oils by glass capillary gas chromatography/mass spectrometry

Glass capillary gas chromatography/mass spectrometry is used to profile Alaskan crude oil for purposes of origin verification. Alaskan oil, sampled at Valdez, Alaska, and transshipped to the U.S. East Coast, is compared with 21 samples of foreign crude oil using GC/MS techniques in which original data is reconstructed at selected parent and fragment ions to generate a series of chromatographic profiles. Comparison of selected profiles and compositional parameters derived from peak ratios allows distinction of Alaskan oil from many foreign crudes and may be applied to the examination of crude mixtures.     

Chromatographic investigations on biodegraded crude oils

Summary Microorganisms have been isolated from a biodegraded crude oil from the Gifhorn trough, Lower Saxony. A non-degraded crude oil, related to the same source rock as the biodegraded one, was inoculated with the microorganisms found and the course of biodegradation thus initiated was followed by gas and liquid chromatographic techniques. The influence of biodegradation on commonly used oil-to-oil correlation parameters was investigated in detail.Originally presented at the 15th International Symposium on Chromatography, Nürnberg, October 1984.     

GC-MS headspace analysis of the volatile components of soya oil without heating the sample

The analysis of volatile compounds, and particularly of certain hydrocarbons, e.g. pentane, and some aldehydes, e.g. hexanal, has been used to estimate the degree of oxidation of vegetable oil. We have tested a dynamic headspace technique without heating the sample during the purge time of the analysis. Some tests have been performed after heating the sample at 180°C for a specified time before the analysis, to compare the results of analysis with and without heating. The best results were obtained at room temperature.     

Identification of 19 phthalic acid esters in dairy products by gas chromatography with mass spectrometry

A detection method for 19 kinds of phthalic acid ester compounds analyzed by n‐hexane/ether/acetonitrile 1:7:8 v/v/v mixed solvent extraction, quick, easy, cheap, effective, rugged, and safe purification and internal standard method of quantitative gas chromatography with mass spectrometry was established. This method can effectively remove interfering materials, such as lipids, fatty acids, and pigments, from dairy products. The 19 kinds of phthalic acid ester compounds were within a 0.025–0.2 mg/kg range, the recovery rate was 65.2–125.7%, relative standard deviation was 7.9–15.4% (n = 6), and the limit of detection was 0.005–0.02 mg/kg. Concentrations of the 19 kinds of phthalic acid ester compounds ranged between 0.01 and 0.12 mg/kg in ten dairy materials and 20 dairy products. The established method is simple, rapid, accurate, and highly sensitive.     

Characterization and purification of fatty acid methyl esters from the liver oil of the deep sea shark (Centrophorus squamosus) by gas chromatography-mass spectrometry and countercurrent chromatography

Summary In the course of our studies on the location of marine products, we have directed our attention to the saponifiable fraction of the liver oil from the deep sea shark (Centrophorus squamosus). Different analytical and preparative techniques, such as high-performance liquid chromatography (HPLC), countercurrent chromatography (CCC), and gas chromatography-mass spectrometry [GC-MS, electron impact (EI) and positive-ion chemical ionization (PCI)] were used. These methods allowed us to characterize, after various derivatizations, most of the fatty acids formed after the saponification of the oil, and to purify two of them, namely: docosahexaenoic acid (DHA or 226) and docosamonoenoic acid (DMA or 221).     

Feasibility of ultra-high performance liquid and gas chromatography coupled to mass spectrometry for accurate determination of primary and secondary phthalate metabolites in urine samples

Phthalates (PAEs) are ubiquitous toxic chemical compounds. During the last few years, some phthalate metabolites (MPAEs) have been proposed as appropriate biomarkers in human urine samples to determine PAE human intake and exposure. So, it is necessary to have fast, easy, robust and validated analytical methods to determine selected MPAEs in urine human samples. Two different instrumental methods based on gas (GC) and ultra-high performance liquid (UHPLC) chromatography coupled to mass spectrometry (MS) have been optimized, characterized and validated for the simultaneous determination of nine primary and secondary phthalate metabolites in urine samples. Both instrumental methods have similar sensitivity (detection limits ranged from 0.03 to 8.89 pg μL⁻¹ and from 0.06 to 0.49 pg μL⁻¹ in GC–MS and UHPLC–MS², respectively), precision (repeatability, expressed as relative standard deviation, which was lower than 8.4% in both systems, except for 5OH-MEHP in the case of GC–MS) and accuracy. But some advantages of the UHPLC–MS² method, such as more selectivity and lower time in the chromatographic runs (6.8 min vs. 28.5 min), have caused the UHPLC–MS² method to be chosen to analyze the twenty one human urine samples from the general Spanish population. Regarding these samples, MEP showed the highest median concentration (68.6 μg L⁻¹), followed by MiBP (23.3 μg L⁻¹), 5cx-MEPP (22.5 μg L⁻¹) and MBP (19.3 μg L⁻¹). MMP (6.99 μg L⁻¹), 5oxo-MEHP (6.15 μg L⁻¹), 5OH-MEHP (5.30 μg L⁻¹) and MEHP (4.40 μg L⁻¹) showed intermediate levels. Finally, the lowest levels were found for MBzP (2.55 μg L⁻¹). These data are within the same order of magnitude as those found in other similar populations.