A comparative study of solvent extraction of total petroleum hydrocarbons in soil
Original Paper First Online: 06 February 2007 Received: 10 August 2006 Accepted: 16 November 2006 Abstract.
Three non-specific methods for the extraction of total petroleum hydrocarbons (TPH) from soil into organic solvent were compared. The techniques used for sample preparation were Soxhlet extraction, closed-vessel microwave-assisted extraction, and CEN shake extraction. The total concentrations of extracted compounds in the boiling point range of C10–C40 were determined by gas chromatography with flame ionization detection. The best recovery (99%) and repeatability (±3%) from standard oil mixtures were obtained with microwave-assisted extraction. However, the different extraction methods exhibited different behaviour when spiked soil samples were extracted. The best repeatability was obtained with CEN shake extraction (±6%) but the repeatability values for Soxhlet and microwave-assisted methods were quite high (>20%). However, the larger uncertainties of the latter extraction methods does not necessarily limit the applicability of these methods to the determination of petroleum hydrocarbons in soil, as in the assessment of soil contamination the expanded uncertainty of the result is usually not limited by analytical uncertainty, but rather by the uncertainty of the primary sampling stage. However, distinctive variation found in the chromatographic profiles illustrates that discretion should be obeyed when chromatograms obtained after application of different extraction methods on petroleum contaminated samples are to be used in the fingerprinting or age dating studies. Otherwise, misleading conclusions concerning the age of spillage could be drawn.
Key words: Total petroleum hydrocarbons (TPH); GC-FID; extraction recovery; soil matrix; fingerprinting. References
Ocean Studies Board, Division of Earth and Life Studies, Marine Board, Transportation Research Board, National Research Council (2002) Spills of Emulsified Fuels: Risks and Response. National Academy Press, Washington D.C.
Google Scholar Dean, J R 1998Extraction methods for environmental analysis John Wiley & Sons Chichester 123 Google Scholar Hartonen, K, Bøwadt, S, Dybdal, H P, Nylund, K, Sporring, S, Lund, H, Oreld, F 2002 Nordic laboratory intercomparison of supercritical fluid extraction for the determination of total petroleum hydrocarbon, polychlorinated biphenyls and polycyclic aromatic hydrocarbons in soil J Chromatogr A 958 239 PubMed CrossRef Google Scholar Hartonen, K 1999Supercritical fluid extraction and pressurized hot water extraction novel environmentally friendly analytical techniques University of Helsinki Helsinki Google Scholar
CEM Corporation (2000) Microwave-accelerated reaction system, Model MARS-X, for the extraction of organic pollutants from solid matrices. Environmental technology certification program, evaluation report. CEM corporation, Matthews, North Carolina
Google Scholar Yang, Y, Hawthorne, S B, Miller, D 1995 Comparison of sorbent and solvent trapping after supercritical fluid extraction of volatile petroleum hydrocarbons from soil J Chromatogr A 699 265 CrossRef Google Scholar Letellier, M, Budzinski, H, Belloq, J, Connan, J 1999 Focused microwave-assisted extraction of polycyclic aromatic hydrocarbons and alkanes from sediments and source rocks Org Geochem 30 1353 CrossRef Google Scholar Flotron, V, Houessou, J, Bosio, A, Delteil, C, Bermond, A, Camel, V 2003 Rapid determination of polycyclic aromatic hydrocarbons in sewage sludges using microwave-assisted solvent extraction. Comparison with other extraction methods J Chromatogr A 99 175 CrossRef Google Scholar Prevot, A B, Gulmini, M, Zelano, V, Pramauro, E 2001 Microwave-assisted extraction of polycyclic aromatic hydrocarbons from marine sediments using nonionic surfactant solutions Anal Chem 73 3790 CrossRef Google Scholar Speight, J G 1999The chemistry and technology of petroleum Marcel Dekker New York Google Scholar Grall, A, Leonard, C, Sacks, R 2000 Peak capacity, peak-capacity production rate, and boiling point resolution for temperature programmed GC with very high programming rates Anal Chem 72 591 PubMed CrossRef Google Scholar Miñones Vázquez, M, Vázquez Blanco, M E, Muniategui Lorenzo, S, López Mahía, P, Fernández Fernández, E, Prada Rodríquez, D 2001 Application of programmed temperature split/splitless injection to the trace analysis of aliphatic hydrocarbons by gas chromatography J Chromatogr A 919 363 PubMed CrossRef Google Scholar Cavagnino, D, Magni, P, Zilioli, G, Trestianu, S 2003 Comprehensive two-dimensional gas chromatography using large sample volume injection for the determination of polynuclear aromatic hydrocarbons in complex matrices J Chromatogr A 1019 211 PubMed CrossRef Google Scholar
ISO 9377-2:2000 (2000) Water quality, determination of hydrocarbon oil index, part 2: method using solvent extraction and gas chromatography. ISO, Geneva Switzerland
prEN 14039:2004:E (2004) Characterization of waste – determination of hydrocarbon content in the range of C10 to C40 by gas chromatography. European Committee for Standardization, Brussels
ISO/DIS 16703:2004 (2004) Soil quality – determination of content of hydrocarbon in the range C10 to C40 by gas chromatography. ISO, Geneva Switzerland
Daling P S, Faksness L G (2002) Laboratory and reporting instructions for the CEN/BT/TF 120 Oil spill identification – Round Robin test – May 2001. SINTEF Applied chemistry, Trondheim, Norway
American Petroleum Institute (1987) Proceedings, sampling and analytical methods for determining petroleum hydrocarbons in groundwater and soil. HESD, Dept. Rpt. #214, American Petroleum Institute, Washington D.C.
Google Scholar Halling, K, Bielsen, K B, Madsen, J, Eriksen, L L H, Klausen, H S, Weibel, N, Andersen, J, Knudsen, K, Wendelbo, T 2004Vurdering af metoder til analyse af olie i jord Miljøstyrelsen Denmark Google Scholar
U.S. Environmental Protection Agency EPA Methods 3540C, 3541, 3545, 3550B, 3560, 4030, 8270C, 8275A, 8440, Test methods for evaluating solid waste, physical/chemical methods: EPA Publication SW-846. Electronic Resources of EPA test methods,
Government of British Columbia, Ministry of Water, Land and Air Protection (2005) Extractable petroleum hydrocarbons in solids by GC/FID. British Columbia Environmental Laboratory Manual. Ministry of Environment, Government of British Columbia, Canada
American Society for Testing and Materials (1990a) Standard practice for oil spill identification by gas chromatography and positive ion electron impact low resolution mass spectrometry american society for testing and materials. W. Conshohocken, PA, USA
American Society for Testing and Materials (1990b) Standard test methods for comparison of waterborne petroleum oils by gas chromatography. American society for testing and materials. W. Conshohocken, PA, USA
Daling P S, Faksness L G (2001) Laboratory and reporting instructions for the CEN/BT/TF/120 Oil Spill Identification – Round Robin Test. Sintef Applied Chemistry, Norway
Malle H (2002) Interlaboratory Study of the Canadian Council for Ministers of the Environment (CCME) Method for the analysis of petroleum hydrocarbons in soil. Environment Canada, National Laboratory for Environmental Testing, National Water Research Institute, Burlington, Ontario
Laitinen A (1999) Supercritical fluid extraction of organic compounds from solids and aqueous solutions. Technical Research Centre of Finland, Espoo
Google Scholar Lopez-Avila, V, Young, R 1994 Microwave-assisted extraction of organic compounds from standard reference soils and sediments Anal Chem 66 1097 CrossRef Google Scholar
Bøwadt S, Dybdahl H P, Bennetzen S, Merry J, Andersen K J, Vejbøl J (2000) Udvikling af analysemetode til bestemmelse af Polycykliske Aromatiske Hydrocarboner (PAH’er) i jord. DHI, Institut for Vand og Miljø, Denmark
Teknologiudviklingsprogrammet for jord- og grundvandsforurening (2004) Vurdering af metoder til analyse af olie i jord. Miljøstyrelsen, Danmark
U.S. Environmental Protection Agency (1996) EPA 3540C. Soxhlet extraction. Revision 3
Google Scholar Squire, S, Ramsey, M H, Gardner, M J 2000 Collaborative trial in sampling for the spatial delineation of contamination and the estimation of uncertainty Analyst 125 139 CrossRef Google Scholar Ramsey, M H, Argyraki, A, Thompson, M 1995 On the collaborative trial in sampling Analyst 120 2309 CrossRef Google Scholar Saari, E 2004Näytteenoton epävarmuus arvioitaessa maa-alueen pilaantuneisuutta University of Oulu Oulu Google Scholar
Puolanne J, Pyy O, Jeltsch U (1994) Saastuneet maa-alueet ja niiden käsittely Suomessa. Saastuneiden maa-alueiden selvitys- ja kunnostusprojekti. Ympäristöministeriö, Helsinki
Christensen B, Larsen T H (1996) Method for determining the age of diesel oil spills in the soil. Ground Water Monit Rem Fall 113
Google Scholar Wade, M J 2001 Age-dating diesel fuel spills: using the european empirical time-based model in the USA Environmental Forensics 2 347 CrossRef Google Scholar Wang, Z, Fingas, M W 2003 Development of oil hydrocarbon fingerprinting and identification techniques Mar Pollut Bull 47 423 PubMed CrossRef Google Scholar