Cold Vapor Atomic Absorption Determination of Hg in Crude Oil and Gasoline Samples after Solid Phase Extraction Using Modified Disks

Document Type: Research Article


1 Department of Chemistry, Payame Noor University, P.O. Box 19395-3697 Tehran, I.R. IRAN

2 Environment and Energy Laboratory, Bonyan Energy Alborz Company, Tehran, I.R. IRAN

3 Faculty of Chemistry, Kharazmi University, Tehran, I.R. IRAN


A facile and highly efficient method have been developed for the preconcentration of the mercury content in crude oil and gasoline samples after digestion with microwave-assisted digestion. Octadecyl silica membrane disk has been modified by the recently synthesized triazene ligand, (E)-1-(2-ethoxyphenyl)-3-(4-nitrophenyl) triaz-1-ene (ENT), then the modified membrane was used for the preconcentration of mercury(II) ions and Cold Vapor Atomic Absorption Spectrometry (CV-AAS) have been used to determine the Hg (II) ion. Solution studies of ENT with a series of metal ions have been done in advance, and the results showed a strong affinity of ENT to the mercury ion. For solid phase extraction, pH of sample 6.0, flow rates 3.0 mL / min, enrichment factor 240, capacity of modified disk 690 µg Hg per 8.0 mg of ligand, eluent solvent 5.0 mL, 1.5M HClO4, and the amount of the ligand 8.0 – 10.0 mg, have been optimized. A linear calibration curve has been obtained in the range of 0.80 – 65 µg / L with R2 = 0.9991 and the Limit Of Detection (LOD) based on three times the standard deviation of the blank was 0.25 µg / L. The Relative Standard Deviation (RSD) for the determination of 50 mL aqueous solution containing 0.5 µg / LHg (II) found to be 1.0 % while a RSD value of 1.9% have been obtained for the determination of 0.1 µg / L Hg (II) (n=3). The characteristic concentration is 1.2 µg / Lin the original samples. The newly developed method was successfully applied to the determination of mercury ion in real crude oil samples, which are very important in environment and industries process.


Main Subjects

[1] Tissot B.P., Welte D.H., "Petroleum Formation and Occurrence", 1st ed. Springer-verlag, Berlin, (1984).

[2] Soin A.V., Maryutina T.A., Arbuzova T.V., Sample Preparation in the Determination of Metals in Oil and Petroleum Products by ICP MS, Journal of Analytical Chemistry., 65(6: 571-576 (2010).

[3] Wilhelm S.M., An Estimate of Mercury Emission to the Atmosphere from Petroleum, Environ. Sci. Tech., 35(24): 4704-4710 (2001).

[4] Wilhelm S.M., Bloom N., Mercury in Petroleum, Fuel Processing Technology, 63, p. 1 (2000).

[5] Wilhelm S. M., Liang L., Kirchgesser D., Identification and Properties of Mercury Species in Crude Oil, Energy Fuel., 20: 180-186 (2006).

[6] Leeper J. E., Mercury-LNG’s Problem, Hydrocarbon Process., 59: 237-240 (1980).

[7] Leeper J. E., Mercury Corrosion in Liquefied Natural Gas Plants, Energy Process., 73: 46-51 (1981).

[8] Sarrazin P., Cameron C. J., Barthel Y., Morrison M.E.,  Processes Prevent Detrimental Effects from As and Hg in Feedstock’s, Oil and Gas Journal., 91: 25 (1993).

[9] Park S. M., Choi H. S., Sensitized Spectrophotometric Determination of Trace Hg (II) in Benzalkonium Chloride Media, Anal. Chim. Acta., 459: 75-81 (2002).

[11] Faraji M., Yamini Y., Rezaee M., Extraction of Trace Amounts of Mercury with Sodium Dodecyl Sulfate-Coated Magnetic Nanoparticles and Its Determination by Flow Injection Induction Inductively Coupled Plasma-Optical Emission Spectrometry,  Talanta.,81: 831 (2010).

[12] Oksana O., Mietek J., Ordered Mesoporous Silica with 2,5-Dimercapto-1, 3, 4- Thiazole Ligand: High Capacity Adsorbents for Mercury Ions, Chem. Commun., 11, p. 205 (2005).

[13] Manzoori J.L., Sorouraddin M.H., Haji Shabani A.M., Determination of Mercury by Cold Vapor Atomic Absorption Spectrometry after Preconcentration with Dithizone Immobilized on Surfactant-coated Alumina, J. Anal. Atom. Spectrom., 13: 305-308 (1998).

[14] Devi P.R., Gangaiah T., Naidu G.R.K., Determination of Trace Metals in Water by Neutron Activation Analysis after Preconcentration on a Poly(acrylamidoxime) Resin,, Anal. Chim. Acta., 249: 533-537(1991).

[15] Ferrua N., Cerutti S., Salonia J.A., Olsina R.A., Martinez L. D., On-Line Preconcentration and Determination of Mercury in Biological and Environmental Samples by Cold Vapor Atomic Absorption Spectrometry, J. Hazard. Mater., 141: 693-699 (2007).

[20] Osborne S. P., Quantitation of Mercury in Petroleum by ETV-ICP-MS, Appl. Spectrosc., 44: 1044-1046 (1990).

[21] Liang L., Lazoff S., Horvat M., Swain E., Gilkeson J., Determination of Mercury in Crude Oil by In-situ Thermal Decomposition Using a Simple Lab Built System, Fresenius, J. Anal. Chem., 367: 8-11 (2000). 

[22] Shafawi A., Ebdon L., Foulkes M., Stockwell P., Corns W., Determination of Total Mercury in Hydrocarbons and Natural Gas Condensate by Atomic Fluorescence Spectrometry, Analyst.,124: 185-189 (1999).

[23] Turunen M., Pera¨niemi S., Ahlgren M., Westerholm H., Determination of Trace Elements in Heavy Oil Samples by Graphite Furnace and Cold Vapor Atomic Absorption Spectrometry after Acid Digestion,  Anal. Chim. Acta., 311: 85-91 (1995).

[24] Liang L., Horvart M., Danilchik P., A Novel Analytical Method for Determination Levels of Total Mercury in Gasoline and other Petroleum Based products, Sci.Total. Environ. 187: 57-64 (1996).

[27] Saracoglu S., Soylak M., Elci L., Enrichment and Separation of Trace of Cadmium, Chromium, Lead and Manganese Ion in Urine by using Magnesium Hydroxide Co Precipitation Method, Trace Elem. Electrolytes, 18: 129- (2001).

[31] Soylak M., Elci L., Dogan M., Flame Atomic Absorption Spectrometric Determination of Cadmium, Cobalt, Copper, Lead and Nickel in Chemical Grade Potassim Salts after an Enrichment and Separation Procedure, J. Trace Microprobe Tech., 17: 149 (1999).

[35] Rofouei M.K., Shamsipur M., Payehghadr M., Crystal Structure of Triazene-1, 3-di (2-Methoxyphenyl), Anal. Sci., 22: 79- (2006).

[36] Smith F. E., Arsenault E. A., Microwave-assisted Sample Preparation in Analytical Chemistry, Talanta., 43: 1207-1268 (1996).

[37] Mohammadi M., Khodadadian M., Rofouei M. K., Novel Palladium (II) Selective Membrane Electrode Based on 4-[(5-Mercapto-1, 3, 4-thiadiazol-2-ylimino)-methyl] Benzene-1, 3-Diol, Collect. Czech. Chem. Commune., 75: 563-575 (2010).

[38] Brandao G.P., Campos R. C.D., Luna A.S., Determination of Mercury in Gasoline by Cold Vapor Atomic Absorption Spectrometry with Direct Reduction in Micro Emulsion Media, Spectrochim. Acta B., 60: 625-631 (2005).

[39] Torres D.P., Dittert I.M., Höhn H., Frescura V.L.A., Curtius A. J., Determination of Mercury in Gasoline Diluted in Ethanol by GF-AAS after Cold Vapor Generation, Preconcentration in Gold Column and Trapping on Graphite Tube, Microchem. J., 96: 32-36 (2010).