New approach to study of spilled crude oils using high resolution GC-MS (SIM) and metastable reaction monitoring GC-MS-MS

Polycyclic aromatic hydrocarbons (PAHs) and geochemical biomarkers are good environmental markers to study the origin and evolution of an oil spill. To have access to the greatest number of molecular ratios, no fractionation of oil into aliphatic and aromatic compounds is made. Three analytical MS approaches are tested to analyze markers in this total hydrocarbon fraction: classical quadrupole GC-MS, high resolution GC-MS (HR GC-MS) and metastable reaction monitoring GC-MS-MS (MRM GC-MS-MS). This analytical approach is used to follow the evolution of PAHs in petroleum polluted mangrove soils over 8 years by using molecular ratios between polycyclic aromatic hydrocarbons and tri- and tetracyclic terpanes.     

Analysis of soil organic matter biomarkers by sequential chemical degradation and gas chromatography-mass spectrometry

Low molecular weight (LMW) biomarkers can be used to trace the source and stage of soil organic matter. However, methods that selectively isolate these groups of compounds are underdeveloped. In this study, we isolate biomarkers by a successive series of extraction and chemical degradation procedures involving solvent extraction (TSE), base (BHY) and acid hydrolysis (AHY), and CuO oxidation (CUO). GC-MS was used to analyze these fractions and the extraction methods were verified by solid-state 13C NMR spectroscopy. The GC-MS response was high for the BHY products (96%), intermediate for the TSE (30%) and CUO (19%), but very low for the AHY fraction (5%) indicating that the fractions contain polar or high molecular weight compounds. Aliphatic lipids (62%), phenols and benzyls (17%) were the predominant classes, accompanied by minor abundances of mono- and disaccharides, LMW acids, terpenoids, steroids, amino acids, and amino sugars. The TSE and BHY fractions contained mainly aliphatic lipids derived from plant waxes, cutin, and suberin. Lignin-derived phenols are the major products in the CUO fraction, and amino compounds and carbohydrates of various sources were identified in the AHY products. The sequential degradation method is useful for the isolation and identification of apolar, LMW biomarkers in soil.     

Improving GC-MS screening analysis by functional-group-related silica gel fractionation of industrial wastewater extracts

The separation of the components of complex industrial waste water extracts according to their functional groups has been accomplished by use of small silica gel columns eluted with a hexane – dichloromethane – methanol gradient. The six fractions obtained covered a polarity range from aliphatic fatty acids to (aromatic) polyhydroxy and polyether compounds. Recovery of model compounds was between 75 and 105%. Used prior to GC-MS analysis this fractionation substantially enhances chromatographic resolution and facilitates peak identification. The procedure was exemplarily applied to an extract of anaerobically treated tannery waste water. Phenols, aromatic acids, and aromatic and aliphatic (poly)hydroxy acids, in the low ppm range, were determined as main constituents. Since fractionation extends the range of detection, trace substances such as chlorocresol, dichlorobenzoic acid, mercaptobenzothiazole, and mercaptoacetic acid were also detectable at the ppb level.     

Isolation of neutral and acidic lipid biomarker classes for compound-specific-carbon isotope analysis by means of solvent extraction and normal-phase high-performance liquid chromatography

An analytical method for the quantitative determination of neutral and acidic lipid biomarkers in particulate and sediment samples has been developed. The method involves a first step with solvent extraction to isolate the neutral from the acidic compounds and a second step using normal-phase HPLC on a Nucleosil silica column to separate four different classes of neutral compounds: (1) aliphatic hydrocarbons, (2) aromatic hydrocarbons, (3) ketone compounds and (4) sterol and alcohol compounds. Recoveries of the individual spiked lipid biomarkers for the whole analytical procedure ranged from 88 to 106% for fatty acids, from 50 to 60% for aliphatic hydrocarbons (> or = n-C17), from 50 to 60% for polycyclic aromatic hydrocarbons (PAHs) (> or = 3 rings), 83% for friedelin and 60-80% for the sterol and alcohol compounds. The isolated compound classes were analysed by gas chromatography-combustion-isotope ratio mass spectrometry to measure the stable carbon isotope ratios in the individual compounds. The method enables the isolation of compound classes without fractionation for compound-specific carbon isotope analysis (delta13C). This analytical protocol has been applied, and proved suitable, for the determination of lipid biomarkers (sterols, fatty alcohols and fatty acids) in marine particulate material and for the determination of PAHs in sediment samples.     

Advanced TMAH and TMAAc thermochemolysis–pyrolysis techniques for molecular characterization of size-separated fractions from aquatic dissolved organic matter

The structural similarities and differences between the original DOM and the eight size fractions separated were studied in detail with the pyrolysis technique in combination with gas chromatography and mass spectrometry (Py-GC-MS) using two alkylating reagents: TMAH (tetramethylammonium hydroxide), to find both esterified and free carboxylic acids; and TMAAc (tetramethylammonium acetate), to specify only free carboxylic acids. A statistical analysis of the original multidimensional TMAH and TMAAc pyrograms disclosed that the overall structural compositions of the five most important size fractions, accounting for 84% of the original DOM, greatly resembled each other. The remaining three minor size fractions were not classified as homogeneous associations, but they also contained the same total, covalently bound and free carboxylic acid species as the other size fractions and the original DOM mixture, thus representing some kind of intermediate forms. This fundamental outcome strongly supports the opinion that the native dissolved humic-like macromolecules resemble supramolecular associations of smaller molecular size moieties with similar structural functionalities. The concentrations of free aliphatic and aromatic dicarboxylic acids in the DOM solution were so low that their effects on the potential formation of multiply charged ions in electrospray ionization-MS (ESI-MS) studies are likely insignificant.     

Method development for fingerprinting of biodiesel blends by solid-phase extraction and gas chromatography-mass spectrometry

A method based on the combination of solid-phase extraction (SPE) with gas chromatography-mass spectrometry (GC/MS) for detailed chemical fingerprinting of biodiesel/petrodiesel blends was developed in the present study. Forensic identification, commonly referred to as chemical fingerprinting, is based on the relative distributions of individual aliphatic hydrocarbons, aromatic hydrocarbons, fatty acid alkyl esters, and free sterols. Fractionation of fuel samples is optimized for the separation of fatty acid esters and free sterols from petroleum hydrocarbons into four fractions: aliphatic, aromatic, fatty acid ester, and polar components. The final recoveries of aliphatic and aromatic hydrocarbons were determined to be in the range of 65-103%, 73-105% for FAMEs, and 78-103% for free sterols in the polar fraction. Excellent separation with negligible crossover of components with different polarities between fractions was observed. Quantitative analysis of blend levels and individual chemical distribution were achieved. The method has great potential for the identification of biodiesel in diesel fuel blends and could form the basis of a method for characterization of biodiesel-contaminated environmental samples.     

Characterisation of varnishes used in violins by pyrolysis-gas chromatography/mass spectrometry

The correct characterisation and a detailed knowledge of the materials originally used in violin varnishes, like natural resins, is crucial for the conservation in museums and for a suitable restoration technique. The study presented here reports on the potential of pyrolysis (Py) coupled with gas chromatography (GC) and mass spectrometry (MS) for the identification of chemical markers of each resin; this technique is very sensitive and selective, it needs a small quantity of sample and does not require chemical treatments. To improve the chromatographic behaviour of polar compounds the derivatising agent tetramethylammonium hydroxide (TMAH) in combination with pyrolysis has been used, in the so-called TMAH thermochemolysis or thermally assisted hydrolysis and methylation (THM), or more simply pyrolysis-methylation. The natural resins studied were colophony, sandarac, manila copal, elemi, amber and benzoin, mainly composed of terpenic compounds, with the exception of the latter, composed of aromatic compounds. Many compounds were identified; in particular, methyl esters of resinous acids that, individually or in a group, can be used as chemical markers. However, through this technique it was not possible to distinguish between the sandarac and manila copal resins because their chromatographic behaviour is very similar. Finally, the procedure applied has been employed in the characterisation of original varnish samples.     

Chemical characterization of aromatic compounds in extra heavy gas oil by comprehensive two-dimensional gas chromatography coupled to time-of-flight mass spectrometry

Comprehensive two-dimensional gas chromatography coupled to time-of-flight mass spectrometry (GC×GC-TOFMS) was used for the characterization of aromatic compounds present in extra heavy gas oil (EHGO) from Brazil. Individual identification of EHGO compounds was successfully achieved in addition to group-type separation on the chromatographic plane. Many aromatic hydrocarbons, especially polycyclic aromatic hydrocarbons and sulfur compounds, were detected and identified, such as chrysenes, phenanthrenes, perylenes, benzonaphthothiophenes and alkylbenzonaphthothiophenes. In addition, triaromatic steroids, methyl-triaromatic steroids, tetrahydrochrysenes and tetraromatic pentacyclic compounds were present in the EHGO aromatic fractions. Considering the roof-tile effect observed for many of these compound classes and the high number of individual compounds identified, GC×GC-TOFMS is an excellent technique to characterize the molecular composition of the aromatic fraction from EHGO samples. Moreover, data processing allowed the quantification of aromatic compounds, in class and individually, using external standards. EHGO data were obtained in μgg(-1), e.g., benzo[a]pyrene were in the range 351 to 1164μgg(-1). Thus, GC×GC-TOFMS was successfully applied in EHGO quantitative analysis.     

Comparing the weathering patterns of six oils using 3-way generalized Procrustes rotation and matrix-augmentation principal components

A case study is presented in which advanced chemical fingerprinting and data interpretation techniques are used to characterize and compare the weathering processes of six oil spillages made under controlled conditions (including the heavy oil released after the Prestige tanker sunk off the Galician coast-NW Spain on 2002). A tiered analytical approach using gas chromatography-flame ionization detection (GC-FID) and gas chromatography-mass spectrometry (GC-MS) was applied along with two different approaches for 3-way analyses; namely, generalized Procrustes rotation, and matrix-augmented principal components analysis. Results showed that the two 3-way chemometric techniques leaded to essentially the same conclusions when analyzing three sets of compounds fingerprinting the spilled hydrocarbons (aliphatic hydrocarbons, polycyclic aromatic hydrocarbons (PAHs) and a set of diagnostic ratios). A steady evolution on the weathering of the oils was observed with both techniques, but for the diagnostic ratios. The variables involved on the weathering were the lightest aliphatic hydrocarbons and a general combination of the PAHs, which differentiated mostly among the light and the heavy products (fuel oils).     

Polycyclic aromatic hydrocarbons in C8 isomer aromatic feed: analysis by GC, GC/MS, and GC/FTIR techniques

Polycyclic aromatic hydrocarbons (PAHs), apart from their carcinogenic and mutagenic nature, create many problems in the petrochemical industry due to their tendency toward carbonization. Compounds in C8 aromatic isomer feed are analyzed by means of sample concentration, followed by separation of individual compounds by gas chromatography on a stainless steel OV-101 phase capillary column and identification by gas chromatography/mass spectrometry and gas chromatography/Fourier transform infrared spectroscopy. Various compounds belonging to different classes (mainly monocyclic, dicyclic, and tricyclic aromatics), oxygenated aromatics, and aliphatic saturates are quantified in the concentrated hydrocarbon residue of C8 isomer feed. Both unsubstituted and alkyl substituted ring type compounds are present. Concentrations obtained for PAH compounds in the C8 isomer feed range from 0.2 to 0.42 micrograms/mL.     

Modeling diamagnetic and magnetooptic properties of organic compounds with the TOSS-MODE approach

The topological substructural molecular design (TOSS-MODE) approach is used to describe the diamagnetic susceptibility of organic compounds. Two data sets composed of 233 aliphatic and 85 aromatic compounds were studied for which good linear correlations were found. The contributions of many different structural fragments and atomic groups were computed by the current approach. The predictive ability of the models developed was tested by using external prediction sets of compounds of different classes than those used in training. A quantitative model based on the current approach was developed to compute the diamagnetic susceptibility exaltation of aromatic compounds, which is exemplified by the study of polycyclic aromatic hydrocarbons. The rotatory power of organic compounds in a magnetic field was also described by the TOSS-MODE approach. Good linear correlations were obtained for this property in aliphatic and aromatic compounds. The predictive abilities of the models found were tested by external prediction sets for which good correlations between calculated and experimental values are found.     

Molecular characterization of organically-bound sulfur in crude oils. A feasibility study for the application of Raney Ni desulfurization as a new method to characterize crude oils

Five crude oils with varying sulfur contents (0.1 – 4.7%) were characterized on a molecular level for organically-bound sulfur. Aromatic fractions were analyzed by GC-(MS) and asphaltene and polar fractions were analyzed by flash pyrolysis-GC-(MS). The polar fractions were also desulfurized with Raney Ni and the hydrocarbons formed were analyzed by GC-MS. Major sulfur compounds in the aromatic fractions were identified as alkylbenzo- and alkyldiben-zothiophenes. The flash pyrolyzates of the asphaltene contained alkylthiophenes and alkylbenzothiophenes as major compounds, depending on the thermal maturity of the oil. Generally, the sulfur-rich crude oils contained relatively more sulfur compounds. The flash pyrolyzates of polar fractions contained a variety of sulfur compounds (alkylthiolanes, alkylthianes, terpenoid sulfides, alkylbenzothiophenes) with substantial differences between different crude oils. Raney Ni desulfurization of the polar fraction yielded hydrocarbons dominated by n-alkanes, but isoprenoid alkanes, n-alkylcyclohexanes, mid-chain methylalkanes, tricyclic terpanes, hopanes and steranes were also present. These hydrocarbons show a potential to fingerprint crude oils since their distribution patterns are more characteristic than those of the hydrocarbons present in the saturated hydrocarbon fraction.     

分子蒸馏分离废次烟末致香成分及在烟草中的应用

采用分子蒸馏技术对超临界CO₂萃取的废次烟末提取物进行分离,并对馏分进行GC-MS分析。 GC-MS结果显示,三级分子蒸馏(80、120、160 ℃)共鉴定出52种化学组分。 80 ℃轻组分段鉴定出15种,以杂环类为主,占总量的98.91%;其次为酯类,占总量的0.606%。 120 ℃轻组分段鉴定出26种,以杂环类为主,占总量的91.42%;其次为酮类、醇类和烃类,分别占总量的4.16%、2.87%和0.74%。 160 ℃轻组分段鉴定出26种,以醇类为主,占总量的67.97%;其次为杂环类,占总量的11.57%,烃类、醚类、酮类、酯类、醛类分别占总量的7.9%、4.09%、3.77%、2.80%、1.89%。 不同馏分段化合物种类和含量存在明显差异性,充分体现了分子蒸馏选择性富集的特点。 感官评吸表明,80 ℃轻组分和120 ℃轻组分按照质量比8:2调配后,香气质较好,香气量较足,口腔较舒适,有甜香显现,吸味较纯净,评吸结果较为理想。     

Polyvinylacetate Gel Permeation Chromatography of H-Coal Liquids and Model Compounds. Comparison with Rigid Gel,Reversed Phase and Normal Phase Chromatography

Abstract

This paper reports the application of polyvinylacetate gel (Fractogel) for size fractionation of the H-Coal liquids and model aromatic hydrocarbons. The four H-Coal liquids were each divided into three classes according to solubility in hexane, benzene, and pyridine. A model mixture of eight compounds when applied to the Fractogel column yielded four fractions; a similar performance was given by a prepacked, Toyo Soda microparticulate column containing styrene-divinylbenzene copolymer. Regarding the twelve H-Coal solvent fractions, the chromatograms obtained from the Fractogel column were analogous to those from the Toyo Soda column. By making further use of model compounds, the Fractogel results are compared with those obtained from reversed phase chromatography on a Partisil ODS column and those from normal phase chromatography on a LiChrosorb silica column. These comparisons reveal the usefulness in separating certain aromatic hydrocarbons by the Fractogel column. Furthermore, judging from the chromatograms of a hexane-soluble H-Coal fraction obtained by the reversed phase and normal phase methods, the ODS column will complement the Fractogel column in fractionating the H-Coal liquids.     

Analysis of volatile compounds of rosemary honey. Comparison of different extraction techniques

Summary The analysis of the volatile fraction from honey requires the sugar matrix to be separated prior to the analysis by GC-MS. In this study, three extraction techniques, simultaneous extraction-distillation, liquid-liquid extraction and solid-phase extraction, were compared to the extraction of the volatile compounds of a rosemary honey. Analysis of these fractions by gas chromatography—mass spectrometry enabled the tentative identification of up to 122 volatile compounds (alcohols, ketones, aldehydes, acids, esters, terpenes, hydrocarbons, phenol, furan and pyran compounds). SDE extracts were rich in terpenes and esters, while the other two techniques avoided the formation of artefacts due to heating the sample.     

Dimethyl carbonate as a novel methylating reagent for fatty acids in analytical pyrolysis

Dimethyl carbonate (DMC) was investigated as a mild, harmless and odorless reagent for pyrolytic methylation of fatty acids. Soybean oil was selected as test material for its high content of (poly)unsaturated fatty acids. Pyrolyses were performed at 500, 700 and 900 degrees C by means of a heated platinum filament pyrolyser on-line and off-line to the GC-MS apparatus. Methyl esters of palmitic, linoleic, oleic and stearic acid were formed as prominent products from off-line pyrolysis of soybean oil in the presence of DMC and zeolite 13X. Fatty acid methyl esters (FAMEs) were not observed at important levels in the absence of zeolite, while on-line Py-GC-MS experiments resulted principally in the formation of free fatty acids and hydrocarbons. The FAME profiles obtained from the DMC/zeolite off-line pyrolysis were compared to those resulting from tetramethylammonium hydroxide (TMAH) thermochemolysis and BF3-methanol procedure. The observed differences between pyrolysis and methanolysis methods were principally attributed to the thermal degradation of unsaturated fatty acids. The effectiveness of the DMC/zeolite pyrolytic methylation was further demonstrated by the analysis of tripalmitine and soybean seeds.     

Chemical profile and biological potential of non-polar fractions from Centroceras clavulatum (C. Agardh) Montagne (Ceramiales, Rhodophyta)

The present study reports the Gas Chromatography-Mass Spectrometry (GC-MS) evaluation of the hexanes and dichloromethane fractions from extracts of the red alga Centroceras clavulatum (C. Agardh) Montagne. Twenty three compounds were identified, totaling ca. 42% of both fractions (0.18 g mass extract). The main constituents of the fractions were hexadecanoic acid (17.6%) and pentadecanoic acid (15.9%). Several secondary metabolites with interesting biological activity, such as (-)-loliolide, neophytadiene, phytol were identified. In addition, several classes of secondary metabolites, including phenolic compounds (e.g., phenylacetic acid), terpene derivatives, fatty acids, halogenated compound (e.g., 2-chlorocyclohexenol), lignoids, steroids, esters, amides (e.g., hexadecanamide), ketones, carboxylic acids, aldehydes and alcohols were observed. The occurrence of several of these structural classes is described for the first time in this species. The same fractions analyzed by GC-MS, and a separate set of polar fractions, were evaluated against two life cycle stages (epimastigote and trypomastigote forms) of the protozoan Trypanosoma cruzi and against phytopatogenic fungi Cladosporium cladosporiodes and C. sphaerospermum. The dichloromethane fraction was active against both T. cruzi forms (epimastigote IC(50) = 19.1 μg.mL-1 and trypomastigote IC(50) = 76.2 μg.mL-1). The hexanes and ethyl acetate fractions also displayed activity against both fungi species (200 μg) by TLC-bioautography.     

Structure-type separation of diesel fuels by solid phase extraction and identification of the two- and three-ring aromatics by capillary GC-mass spectrometry

A simple and effective solid phase extraction (SPE) method using silica gel micro glass columns has been developed for the separation of diesel fuel into groups of aliphatic, and mono-, di- and polyaromatic hydrocarbons. It is based on a stepwise gradient of dichloromethane in n-pentane. The resulting fractions were analyzed by capillary gas chromatography with a flame ionization detector and coupled gas chromatography-mass spectrometry. Commercially available standards, and retention indices and mass spectra were used for identification of individual aromatic compounds. The principal polycyclic aromatic hydrocarbons (PAHs) in diesel fuel are naphthalene, biphenyl, fluorene, phen-anthrene and their alkylated derivatives. Sulfur-containing PAHs are mainly represented by methyl-substituted dibenzo-thiophenes.     

Nonsaponifiable lipid components of the pollen of elder (Sambucus nigra L.).

Pollen of the elder (Sambucus nigra L.) was extracted with chloroform-methanol. The extract was separated by column chromatography into the following groups of compounds: hydrocarbons (8.7%). polycyclic aromatic hydrocarbons (0.2%), complex esters (5.2%), triglycerides (18.7%), hydroxy esters (27.9%), free fatty acids and alcohols (16.8%), free sterols (6.8%), and triterpenic alcohols (4.0%). The nonsaponifiable components (hydrocarbons, fatty acids, alcohols, and sterols) were examined in detail using spectroscopic and chromatographic methods (IR spectroscopy, GC, and GC-MS). The identified compounds were characterized by their mass spectra and Kováts retention indices. The double bond positions and their configurations in unsaturated compounds are also reported.     

污水污泥流化床气化焦油的化学组成分析

以空气为气化剂、并通过GC-MS分析,研究了污水污泥流化床气化时气化温度（650、750和850 ℃）和污泥性质对污泥气化焦油产率及其化学组成的影响。结果表明,污泥气化焦油产率随气化温度的升高而降低,且厌氧消化污泥气化焦油的产率比未消化污泥的低。污泥气化焦油中的化学组成可分为五类：脂肪族化合物、脂环化合物、芳香烃、芳香烃衍生物和杂环化合物。随气化温度的升高,A²/O工艺的未消化污泥气化生成的焦油中脂肪族化合物和脂环化合物的产率均明显降低,芳香烃衍生物的产率则有显著地提高,而芳香烃和杂环化合物的产率均先增加后减少。气化温度为650 ℃时,活性污泥法消化污泥气化焦油中五类有机物的产率均低于未消化污泥的,而A²/O工艺消化污泥气化焦油中芳香烃产率高于未消化污泥的,其他四种有机物的产率则均低于未消化污泥的。