The detection of high-mass aliphatics in petroleum by matrix-assisted laser desorption/ionisation mass spectrometry.

Rationale: The development of simplified procedures for isolating high-mass alkanes present in crude oils is described. The new procedures, which bypass the sample recovery step with hot toluene in the conventional alkane-isolation procedure, also provide an effective sample preparation route, prior to analysis by matrix-assisted laser desorption/ionisation mass spectrometry (MALDI-MS).

Methods: Urea-alkane adducts are formed by mixing sample and urea solutions on chromatographic paper or silica-coated plates.

Limitations of mass spectrometric methods for the characterization of polydisperse materials.

This paper is a review of work on the characterization of coal liquids and petroleum residues and asphaltenes over several decades in which various mass spectrometric methods have been investigated. The limitations of mass spectrometric methods require exploration in order to understand what the different analytical methods can reveal about environmental pollution by these kinds of samples and, perhaps more importantly, what they cannot reveal. The application of mass spectrometry to environmental problems generally requires the detection and determination of the concentration of specific pollutants released into the environment by accident or design.

Estimating molecular masses of petroleum-derived fractions: High mass (>2000u) materials in maltenes and asphaltenes from Maya crude oil.

Molecular mass ranges and average masses of fractions from a heavy Mexican crude oil (Maya) have been studied, using mainly size exclusion chromatography (SEC) and laser desorption-mass spectrometry (LD-MS). Method development focused on the use of planar chromatography and size exclusion chromatography (SEC), to isolate narrow bands of material from solubility-separated fractions of the crude oil. The procedure provides a planar chromatography based method for studying mass ranges in complex hydrocarbon mixtures.

Molecular mass ranges of coal tar pitch fractions by mass spectrometry and size-exclusion chromatography.

A coal tar pitch was fractionated by solvent solubility into heptane-solubles, heptane-insoluble/toluene-solubles (asphaltenes), and toluene-insolubles (preasphaltenes). The aim of the work was to compare the mass ranges of the different fractions by several different techniques. Thermogravimetric analysis, size-exclusion chromatography (SEC) and UV-fluorescence spectroscopy showed distinct differences between the three fractions in terms of volatility, molecular size ranges and the aromatic chromophore sizes present.

Pyrolysis of waste polypropylene and characterisation of tar.

Waste polypropylene (PP) has been pyrolysed to obtain mainly a liquid tar product of high yield (83.5%) with the balance as gas (15.5%) and a little residue (1.

Separation and measurement of flame-formed high molecular weight polycyclic aromatic hydrocarbons by size-exclusion chromatography and laser desorption/ionization time-of-flight mass spectrometry.

The partial contribution of polycyclic aromatic hydrocarbons (PAH), capable of being detected by gas chromatography (GC-PAH), both to the total mass of the extractable organic fraction of flame-formed carbon particulates and to its UV-visible absorption and fluorescence spectra, has been determined by previous work. This contribution indicates the presence of PAH of molecular weight (MW) greater than 400 Da not accessible to conventional analysis. The detection of species in this higher MW range is important for both their potential toxicology and their possible role in soot formation.

Examination of soil contaminated by coal-liquids by size exclusion chromatography in 1-methyl-2-pyrrolidinone solution to evaluate interference from humic and fulvic acids and extracts from peat.

Soil from a redundant coke oven site has been examined by extraction of soluble materials using 1-methyl-2-pyrrolidinone (NMP) followed by size exclusion chromatography (SEC) of the extracted material. The extracted material was found to closely resemble a high temperature coal tar pitch. Standard humic and fulvic acids were also examined since these materials are very soluble in NMP and would be extracted with pitch if present in the soil.

The high-mass component (>m/z 10 000) of coal tar pitch by matrix-assisted laser desorption/ionisation mass spectrometry and size-exclusion chromatography.

The size-exclusion chromatography (SEC) of acetone-soluble, pyridine-soluble and pyridine-insoluble fractions of a coal tar pitch indicates a bimodal distribution in each fraction. The proportion of high-mass material excluded from the SEC column porosity increases with solvent polarity. The polymer calibration of SEC shows the mass range of the small molecules to be from approximately 100 u to approximately 6000 u, with the mass range of the large excluded molecules above 200 000 u and up to several million u.

Estimation of the molecular mass range of the tar from pyrolysis of casein by gas chromatography-mass spectrometry, probe mass spectrometry and size exclusion chromatography with 1-methyl-2-pyrrolidinone as eluent.

Casein has been pyrolysed to obtain a biochar (28.3% yield), with mostly meso- and macro-pore structure, and a liquid tar product of high yield (37.5%) with the balance as gas (20.

Oligomeric carbon and siloxane series observed by matrix-assisted laser desorption/ionisation and laser desorption/ionisation mass spectrometry during the analysis of soot formed in fuel-rich flames.

Oligomeric carbon and siloxane series have been observed by matrix-assisted laser desorption/ionisation mass spectrometry (MALDI-MS), during the analysis of the dichloromethane (DCM)-soluble fractions of condensable material recovered from fuel-rich flames. Laser desorption (LD) spectra showed a pattern of oligomeric dimethyl-siloxane structures with a spacing of 74 u. The siloxane series appears to have originated as contamination of samples by silicone oil used to lubricate connections of polymer tubing.

Thin-layer chromatography of pitch and a petroleum vacuum residue. Relation between mobility and molecular size shown by size-exclusion chromatography.

A coal tar pitch and a petroleum vacuum residue have been separated by TLC using pyridine, acetonitrile, toluene and pentane to develop the chromatograms. The bands of material detected were recovered in 1-methyl-2-pyrrolidinone (NMP) solvent and examined by size-exclusion chromatography (SEC) in NMP eluent. The relation between elution time in SEC and mobility on the TLC plate indicated that molecular size increased steadily with increasing immobility on the plate.

Size-exclusion chromatography of large molecules from coal liquids, petroleum residues, soots, biomass tars and humic substances.

Size-exclusion chromatography (SEC) using 1-methyl-2-pyrrolidinone (NMP) as eluent has been calibrated using various standard polymers and model compounds and applied to the analysis of extracts of coal, petroleum and kerogens, to petroleum vacuum residues, soots, biomass tars and humic substances. Three separate columns of different molecular mass (MM) ranges were used, with detection by UV absorption; an evaporative light scattering detector was used for samples with no UV absorption. Fractionation was useful to separate signal from the less abundant high-mass material, which was normally masked by the strong signal from the more abundant low-mass material in the absence of fractionation.

Pyrolysis-gas chromatography/mass spectrometry of fractions separated from a low-temperature coal tar: an attempt to develop a general method for characterising structures and compositions of heavy hydrocarbon liquids.

A low-temperature coal tar has been fractionated by column chromatography into acetonitrile, pyridine and 1-methyl-2-pyrrolidinone- (NMP) solubles. The tar and its fractions have been examined by pyrolysis-gas chromatography/mass spectrometry (GC/MS). Fractionation by planar chromatography was also carried out for purposes of comparison.

Study of the polymerization of anthracene oil with AlCl3 by chromatography and related techniques.

The structure and composition of products from the reaction of anthracene oil with anhydrous AlCl3 have been examined. Size-exclusion chromatography has been carried out using a column with polystyrene-polydivinylbenzene as stationary phase, 1-methyl-2-pyrrolidinone at 80 degrees C as eluent and variable-wavelength UV-absorption detection. This system provides a chromatogram of the sample with several peaks.

Structural characterisation of Baltic amber and its solvent extracts by several mass spectrometric methods.

A sample of Baltic amber ( approximately 40 million yrs old) has been extracted using pentane, toluene and 1-methyl-2-pyrrolidinone (NMP). The relationship between solubility characteristics of the extracts in relation to molecular mass and chemical makeup has been investigated. The extracts were first characterised by (13)C-NMR spectrometry, size exclusion chromatography (SEC) and UV-fluorescence spectroscopy.

Pyrolysis-gas chromatography/mass spectrometry of a coal extract and its fractions separated by planar chromatography: correlation of structural features with molecular mass.

The structural characterisation of a coal liquefaction extract and its three fractions separated by planar chromatography has been described. Size exclusion chromatography showed the molecular mass distributions to become progressively larger with decreasing mobility on the plate. UV-fluorescence spectroscopy of the fractions indicated parallel increases in the sizes of polynuclear aromatic ring systems.

Determination of trace elements by inductively coupled plasma mass spectrometry of biomass and fuel oil reference materials using milligram sample sizes.

Most of the analytical techniques used to quantify elements associated with solid samples suffer from high detection limits and cannot be used for trace elements in biomass samples, particularly when only 20 mg are available for analysis. Inductively coupled plasma mass spectrometry (ICP-MS) can achieve detection limits of parts-per-trillion with liquid sample introduction by solution nebulisation. This technique was therefore tested with two standard biomass reference materials: oriental tobacco leaves and cabbage leaves.

Identification of organically associated trace elements in wood and coal by inductively coupled plasma mass spectrometry.

1-Methyl-2-pyrrolidinone (NMP) was used to extract samples of wood (forest residue) and coal; the extracts were analysed by inductively coupled plasma mass spectrometry (ICP-MS) using two different sample preparation methods, in order to identify trace elements associated with the organic part of the samples. A sample of fly ash was similarly extracted and analysed in order to assess the behaviour of the mineral matter contained within the wood and coal samples. 32% of the biomass was extracted at the higher temperature and 12% at room temperature while only 12% of the coal was extracted at the higher temperature and 3% at room temperature.

Determining a 'safe' high-mass limit in matrix-assisted laser desorption/ionisation time-of-flight mass spectra of coal derived materials with reference to instrument noise.

Three methods for determining a 'safe' estimate for high-mass limits of MALDI spectra of coal derived liquids were explored, using a sample of coal-tar pitch and its pyridine-insoluble fraction. Co-addition of increasing numbers of single-shot spectra (10, 30, 50 and 100 pulses) showed visually observable reductions in noise levels, consistent with robust and statistically meaningful signals. Three separate types of post-acquisition calculation were used to identify high-mass limits of the spectra.