Evaluation of Analytical Procedures in the Determination of Trace Metals in Heavy Crude Oils by Flame Atomic Absorption Spectrophotometry

DOI: 10.4236/ajac.2015.64031   PDF   HTML   XML   5,007 Downloads   5,870 Views   Citations


In the present work, four trace metals, V, Ni, Cu and Fe, have been determined in five crude oil samples of Eastern Baghdad area, Iraq by flame atomic absorption spectrophotometry. The crude oils are characterized with API gravity values in the range, 25 - 15. The V/Ni ratios for the studied crudes were in the range 3.7 to 5.4 and indicated a typical of the sapropelic-type organic matter. The Ni and V contents were correlated with API gravity where an increase of metal contents with the decrease in the API values could be observed. The plots of V and Ni versus sulfur indicated linear correlation. This is attributed to the increase of porphyrinic structures of the metals. The method of direct dilution (DD) with organic solvent and the standard addition (SA) were evaluated as compared with standard dry ashing-acid dissolution (DA). In most cases the DD method gave V and Ni concentrations that are higher than DA and for the heavier crude oil (API = 15) the DD results were significantly smaller than those of the DA method. The SA method can be a good solution to determine the trace metals in heavy crude oils provided that the addition must not exceed the levels of the metal concentration in the diluted samples.

Share and Cite:

Barbooti, M. (2015) Evaluation of Analytical Procedures in the Determination of Trace Metals in Heavy Crude Oils by Flame Atomic Absorption Spectrophotometry. American Journal of Analytical Chemistry, 6, 325-333. doi: 10.4236/ajac.2015.64031.

Conflicts of Interest

The authors declare no conflicts of interest.


[1] Elrich, J., Hilner, A. and Stark, H. (1985) Distribution of Trace Elements in Crude Oils from Southern Germany. Chemical Geology, 48, 313-323.
[2] Hitchon, B. and Filby, R.H. (1984) Use of Trace Elements for Classification of Crude Oils into families; Example from Alberta, Canada. American Association of Petroleum Geologists (AAPG) Bulletin, 68, 838-849.
[3] Bakirova, S.F., Kotova, A.V., Yagyayeva, S., Fedorova, N. and Nadirov, N.K. (1984) Structural Features of Vanadyl Porphyrins of Petroleum of West Kazakhstan. Petroleum Chemistry U.S.S.R., 24, 196-202.
[4] Barbooti, M.M., Al-Taee, M.A. and Qasim, B.H. (2010) Electrothermal Atomic Absorption Spectrophotometric Determination of V, Ni and Pb in Hydrocarbon Polluted Soils. Engineer. Technol., 28, 17-28.
[5] Barbooti, M.M., Al-Madfai, S.H. and Al-Sammerrai, D.A. (1986) Thermo-gravimetric Characterization of Quayarah Heavy Crude Oils. Journal of Thermal Analysis, 31, 253-260.
[6] Reynolds, J.G. (2004) Removal of Nickel and Vanadium from Heavy Crude Oils by Exchange Reactions. Preprints of Papers-American Chemical Society, Division of Fuel Chemistry, 49, 79-80.
[7] Chifang, C., Zhuguo, D., Jiamo, F. and Guoying, S. (2005) Determination of Trace Elements in crude Oils and Organic Materials Extracted from Oil-Forming Source Rocks in China by INAA. Journal of Radioanalytical and Nuclear Chemistry, 151, 177-184.
[8] Fischbeck, H.J., Engel, M.H., Ruffel, A.V. and Weaver, B.L. (1987) Application of an External Beam PIXE Method for Determining the Distribution of Trace Metals in Degraded and Nondegraded Crude Oils. Nuclear Instruments and Methods in Physics Research, 24, 655-657.
[9] Tadayon, F., Massoumi, A. and Eslami, M. (1999) Determination of Vanadium, Nickel, and Iron in Crude Oil by High-Performance Liquid Chromatography. Journal of Chromatographic Science, 37, 371-4.
[10] Sebor, G., Lang, I., Vavrecka, P., Sychra, V. and Weisser, O. (1975) The Determination of Metals in Petroleum Samples by Atomic Absorption Spectrometry, Part I., The determination of Vanadium. Analytica Chimica Acta, 78, 99-106.
[11] Botto, R.I. (1987) Matrix Interferences in the Analysis of Organic Solutions by Inductively Coupled Plasma-Atomic Emission Spectrometry. Spectrochimica Acta Part B, 42, 181-199.
[12] Dreyfus, S., Pécheyran, C., Magnier, C., Prinzhofer, A., Lienemann, C.P. and Donard, O.F.X. (2005) Direct Trace and Ultra-Trace Metals Determination in Crude Oil and Fractions by Inductively Coupled Plasma Mass Spectrometry. Journal of ASTM International, 2, 1-8.
[13] Saint’Pierre, T., Dias, L.F., Pozebon, D., Aucelio, R.Q., Curtius, A.J. and Welz, B. (2002) Determination of Cu, Mn, Ni and Sn in Gasoline by Electrothermal Vaporization Inductively Coupled Plasma Mass Spectrometry, and Emulsion Sample Introduction. Spectrochimica Acta Part B, 57, 1991-2001.
[14] De Souza, R.M., Da Silveira, C.L.P. and Aucelio, R.Q. (2004) Determination of Refractory Elements in Used Lubricating Oil by ICP-OES Employing Emulsified Sample Introduction and Calibration with Inorganic Standards. Analytical Sciences, 20, 351-355.
[15] Bettinelli, M. and Tittarelli, P. (1994) Evaluation and Validation of Instrumental Procedures for the Determination of Nickel and Vanadium in Fuel Oils. Journal of Analytical Atomic Spectrometry, 9, 805-812.
[16] Barbooti, M.M. and Jasim, F. (1982) Electrothermal Atomic Absorption Spectrometric Determination of Vanadium. Talanta, 29, 107-111.
[17] Fabec, J.L. and Rushak, M.L. (1985) Determination of Nickel, Vanadium, and Sulfur in Crudes and Heavy Crude Fractions by Inductively Coupled Argon Plasma/Atomic Emission Spectrometry and Flame Photometry. Analytical Chemistry, 57, 1853-1863.
[18] Osuji, L.C. and Onojake, C.M. (2004) Trace Heavy Metals Associated with Crude Oil: A Case Study of Ebocha-8 Oil-Spill-Polluted Site in Niger Delta, Nigeria. Chemistry & Biodiversity, 1, 1708-1715.
[19] Brandao, G.P., De Campos, R.C., De Castro, E.V.R. and De Jesus, H.C. (2007) Determination of Copper, Iron and Vanadium in Petroleum by Direct Sampling Electrothermal Atomic Absorption Spectrpmetry. Spectrochimica Acta Part B, 62, 962-969.
[20] Barbooti, M.M., Zaki, N.S., Baha-Uddin, S.S. and Hassan, E.B. (1990) Use of Silica Gel in the Preparation of Used Lubricating Oils for the Determination of Wear Metals by Flame Atomic Absorption Spectrophotometry. Analyst (London), 115, 1059-1061.
[21] Udoh, A.P., Thomas, S.A. and Ekanem, E.J. (1992) Application of p-Xylenesulphonic Acid as Ashing Reagent in the Determination of Trace Metals in Crude Oil. Talanta, 39, 1591-1595.
[22] Kowalewska, Z. (2007) Effect of Chemical Modification on Behavior of Various Organic Vanadium Forms during Analysis by Electrothermal Atomic Absorption Spectrometry. Spectrochimica Acta Part B, 62, 273-282.
[23] Dittert, I.M., Silva, J.S.A., Araujo, R.G.O., Curtius, A.J., Welz, B. and Becker-Ros, H. (2009) Direct and Simultaneous Determination of Cr and Fe in Crude Oil Using High-Resolution Continuum Source Graphite Furnace Atomic Absorption Spectrometry. Spectrochimica Acta Part B, 64, 537-543.
[24] Sedykh, E.M., Bannykh, L.N., Korobeinik, G.S. and Starshinova, N.P. (2011) Determination of Nickel and Vanadium in Crude Oils by Electrothermal Atomic Absorption Spectrometry and Inductively Coupled Plasma Atomic Emission Spectroscopy after Mineralization in an Autoclave. Inorganic Materials, 47, 1539-1543.
[25] Ortega, G.S., Pécheyran, C., Hudin, G., Marosits, E. and Donard, O.F.X. (2013) Different Approaches of Crude Oil Mineralisation for Trace Metal Analysis by ICPMS. Microchemical Journal, 106, 250-254.
[26] Institute of Petroleum (1989) Standard Methods of Analysis and Testing of Petroleum and Related Products. London Vol. 2, 336.
[27] Institute of Petroleum (1989) Standard Methods of Analysis and Testing of Petroleum and Related Products. London Vol. 1, 160.
[28] Zaki, N.S., Barbooti, M.M., Baha-Uddin, S.S. and Hassan, E.B. (1989) Determination of Trace Metals and Their Distribution in Heavy Crude Oil Distillates (350°C+) by Atomic Absorption Spectrophotometry. Applied Spectroscopy, 43, 1257-1259.
[29] Ali, M.F., Bukhari, A. and Saleem, M. (1983) Trace Metals in Crude Oils from Saudi Arabia. Industrial & Engineering Chemistry Product Research and Development, 22, 691-694.
[30] Must, R.F., Ruch, R.R. and Meents, W.F. (1973) Vanadium in Devonian, Silurian, and Ordovician Crude Oils of Illinois. Illinois State Geological Survey, Urbana, Circular 483.
[31] Carlson, R.M.K., Pena, M.M., Boduszynski, M.M., Rechsteiner, C.E., Shafizadeh, A.S.G. and Henshaw, P.C. (1998) Geochemical-Viscosity Correlations among Heavy Crude Oils of the San Joaquin Valley. California, Paper 1998.203, 7th UNITAR Heavy Crude and Tar Sands International Conference Proceedings.
[32] Barbooti, M.M., Said, E.Z., Hassan, E.B. and Abdul-Ridha, S.M. (1989) Separation and Spectrophotometric Investigations of the Distribution on Nickel and Vandium in Heavy Crude Oils. Fuel, 68, 84-87.
[33] Sebor, G., Kubelka, V. and Weisser, O. (1979) Separation and Characterization of Vanadylporphyrins from Romashkino Petroleum. Collection of Czechoslovak Chemical Communications, 44, 551-557.
[34] Lienemann, C.P., Dreyfus, S., Pécheyran, C. and Donard, O.F.X. (2007) Trace Metal Analysis in Petroleum Products: Sample Introduction Evaluation in ICP-OES and Comparison with ICP-MS Approach. Oil & Gas Science and Technology, 62, 69-77.

comments powered by Disqus

Copyright © 2020 by authors and Scientific Research Publishing Inc.

Creative Commons License

This work and the related PDF file are licensed under a Creative Commons Attribution 4.0 International License.