Petroleum fingerprinting

Johnson, M. D. and Morrison, R. D., 1996, Petroleum Fingerprinting Dating a Gasoline Release Environmental Protection, September, pp. 37-39. 

Petroleum Fingerprinting of Contaminated Soils and Water Using GCFID... 

Lukco, R.G., Kosman, J.J., "The Use of GC-AES Multielement Simulated Distillation for Petroleum Product Fingerprinting , J. Chrom. Set. 1993, March... 

The sulfur compounds that are present in minor quantities in petroleum products also exhibit a typical gas chromatographic fingerprint easily obtained by flame photometric detection. This fingerprint has been introduced to complement the flame ionisation detection chromatogram with the aim of resolving the ambiguities or increasing the reliability in the identification of the pollutants [74]. 

Interpretation/report The GC retention time of a naphthalene standard and the mass spectrum of this peak confirm its presence. Because of the complexity of the chromatograms of the petroleum products and the pesticide sample, you find it impossible to examine the chromatogram of each. However, a comparison of the GC fingerprints (i.e., the matching of chromatographic peaks and comparison of peak ratios) clearly shows that the sample consists of naphthalene dissolved in kerosene. 

Broman et al. [15] have discussed methods of fingerprinting petroleum hydrocarbons in bottom sediments. 

Testa, S. M. and Halbert, W. E., 1989, Geochemical Fingerprinting of Free Phase Liquid Hydrocarbons In Proceedings of the National Water Well Association and American Petroleum Institute Conference on Petroleum Hydrocarbons and Organic Chemicals in Ground Water Prevention, Detection and Restoration, NWWA, Houston, TX, pp. 29-44. 

Furthermore, as a fuel evaporates or biodegrades, its pattern can change so radically that identification becomes difficult. Consequently, a gas chromatographic fingerprint is not a conclusive diagnostic tool. The methods used for total petroleum hydrocarbon analysis must stress calibration and quality control, whereas pattern recognition methods stress detail and comparability. 

Pharr D, McKenzie J, Hickman A. 1992. Fingerprinting petroleum contamination using synchronous scanning fluorescence spectroscopy. Ground Water 30(4) 484-489. 

Boehm, P.D., Douglas, G.S., Burns, W.A., Mankiewicz, P.J., Page, D.S., Bence, A.E., 1997. Advances in petroleum hydrocarbon chemical fingerprinting and allocation techniques after the Exxon Valdez oil spill. Mar. Pollut. Bull. 34, 599-613. 

To identify the type of a petroleum product, laboratories rely on characteristic fingerprints obtained as chromatographic patterns and use petroleum product standards for the pattern recognition and fuel quantitation. That is why TPH results are usually reported in relation to a fuel standard TPH as gasoline, TPH as diesel, TPH as motor oil. 

Petroleum fuel analysis does not require second column or second detector confirmation. Fuels are identified based on their fingerprints or characteristic patterns of multiple peaks similar to ones shown in Figure 2.5. Each peak represents an individual chemical constituent, and each fuel has a unique combination of these constituents forming a characteristic pattern or a fingerprint. The fingerprints obtained... 

The utility of sulfur K-edge X-ray absorption spectroscopy for the determination and quantification of sulfur forms in nonvolatile hydrocarbons has been investigated. X-ray Absorption Near Edge Structure (XANES) spectra were obtained for a selected group of model compounds, for several petroleum asphaltene samples and for Rasa coal. For the model compounds the sulfur XANES was found to vary widely from compound to compound, and to provide a fingerprint for the form of sulfur involved. The use of third derivatives of the spectra enabled discrimination of mixtures of sulfide and thiophenic model compounds, and allowed approximate quantification of the amount of each component in the mixtures, in the asphaltene samples and the coal. These results represent the first demonstration that nonvolatile sulfide and thiophenic sulfur forms can be distinguished and approximately quantified by direct measurement. 

Figure 6 GCMS is a widely used technique in petroleum exploration and production studies. The use of multiple ion detection to obtain the fingerprints for the various classes of biomarkers is an extremely important ancillary GCMS technique. In this diagram the miz 191 and 217 chromatograms show the distributions of the terpanes and...

The concentration of individual biomarkers in a crude oil are relatively low (Peters and Moldowan, 1992 Figure 7), but their information content is significant and related to source, depositional environments, maturity, age, migration, and extent of biodegradation. The complete biomarker fingerprints obtained by MID are used extensively for the purpose of undertaking oil/oU or oil/source rock correlation studies. There are numerous papers and books which have documented the utilization of biomarkers in petroleum exploration only a few examples of the major applications will be... 

Petroleum hydrocarbon sources to North American and worldwide waters were summarized in a report by NRC (2002). In many cases of large petroleum spills, the specihc source of petroleum spill is evident, and no geochemical fingerprinting is required to establish the source. Nevertheless, the inventory of petroleum compounds and biomarkers that are eventually sequestered in bottom sediments need not reflect sole derivation from a single source, even in cases of massive oil spills in the area (e.g., Kvenvolden et al., 1995 Wang et al., 1999). Where a mass balance of petroleum sources is required to properly design remediation or identify a point source, molecular methods for distinguishing sources of hydrocarbons have come to the fore. 

Abdul-KassimT. A. T. and Simoneit B. R. T. (1995) Petroleum hydrocarbon fingerprinting and sediment transport assessed by molecular biomarker and multivariate statistical analysis in the eastern harbour of Alexandria, Egypt. Mar. Pollut. Bull. 30, 63-73. 

In petroleum analyses, and specifically for aviation fuels, there are a good many separations where complete resolution is not needed. GC fingerprinting of different types of fuels (diesel, gasoline, aviation fuels, kerosene, etc.) can be performed quickly to characterize the mixtures in useful ways. Simulated distillation is one good example of... 

Klusman, R.W., Voorhees, K.J., Hickey, J.C. and Malley, M. J., 1986. Application of the K-V fingerprint technique for petroleum exploration. In M.J. Davidson (ed.). Unconventional Methods in Exploration for Petroleum and Natural Gas IV. Southern Methodist University Press, Dallas, pp. 219-243. 

Pyrolysis-GC is being used increasingly in the field of petroleum geochemistry for rapid comparison of samples by fingerprinting. The method used by the Institut Francais du Petrole (Saint-Paul et al., 1980 Durand and Paratte, 1983) has been applied to humic substances in sediments. It is a low-temperature (475°C) pyrolysis with intermediate trapping of the effluent with liquid nitrogen (with the exception of CH4) followed by GC analysis (Dexsil 300 packed column). 

Carbonized coal products have a unique fingerprint by both GC and fluorescence analyses. Both these fingerprints confirm that sediments from the Elizabeth River are contaminated with carbonized coal products and allow for the detection of carbonized coal hydrocarbons, even in the presence of petroleum-derived hydrocarbons. Fluorescence allows for the rapid analysis of more samples and shows the contamination within the Elizabeth River to be widespread. Carbonized coal products in the sediments may constitute a chronic long-term source of PNA s to the water column. 

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